WO2013030977A1 - 樹脂粒子集合体、その製造方法、およびその用途 - Google Patents
樹脂粒子集合体、その製造方法、およびその用途 Download PDFInfo
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- WO2013030977A1 WO2013030977A1 PCT/JP2011/069764 JP2011069764W WO2013030977A1 WO 2013030977 A1 WO2013030977 A1 WO 2013030977A1 JP 2011069764 W JP2011069764 W JP 2011069764W WO 2013030977 A1 WO2013030977 A1 WO 2013030977A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Definitions
- the present invention relates to a resin particle aggregate formed by aggregating a plurality of resin particles made of a polymer of a vinyl monomer, for example, a light diffusing plate used as a component of a liquid crystal display device, optical Resin particle aggregate that can be suitably used as a light diffusing agent for constituting a light diffusing member such as a film (antiglare film, light diffusing film, etc.), lighting cover, etc., its production method, and its use (light diffusing resin) Composition, coating composition, optical film, and external preparation).
- a light diffusing plate used as a component of a liquid crystal display device
- optical Resin particle aggregate that can be suitably used as a light diffusing agent for constituting a light diffusing member such as a film (antiglare film, light diffusing film, etc.), lighting cover, etc., its production method, and its use (light diffusing resin) Composition, coating composition, optical film, and external preparation).
- acrylic cross-linked resin particles and styrenic cross-linked resin particles have been used for light diffusing agents such as lighting covers, light diffusing films for liquid crystal display devices, light diffusing plates, matting agents for paints, etc.
- light diffusing agents such as lighting covers, light diffusing films for liquid crystal display devices, light diffusing plates, matting agents for paints, etc.
- resin particles with functions such as a light diffusing function and a matting function
- a dispersion in which resin particles are dispersed in a binder resin solution is coated on a substrate to form irregularities on the surface (light diffusion film surface or coating film surface).
- the light diffusing function and the matte function can be obtained by the unevenness of the surface.
- the resin particles are kneaded into a transparent base resin such as polycarbonate or polystyrene to form a mixture,
- a transparent base resin such as polycarbonate or polystyrene
- the mixture is formed into a molded body by extrusion molding or injection molding.
- This molded body exhibits a light diffusing function by utilizing the unevenness on the surface of the light diffusing member and the refractive index difference between the transparent base material and the resin particles, and functions as a light diffusing member.
- resin particles having excellent light diffusibility and matte properties resin particles having a relatively small particle size are required.
- resin particles having a small particle diameter are difficult to handle due to the fact that dust tends to fly and fluidity is poor. Then, it is made easy to handle by aggregating (aggregating) a plurality of resin particles using spray drying or the like to form a resin particle aggregate.
- Patent Document 1 includes crosslinked polymer fine particles obtained by polymerizing a vinyl monomer mixture composed of divinylbenzene or trimethylolpropane tri (meth) acrylate and a non-crosslinkable monomer. Fine particle aggregates are described.
- Patent Document 2 a copolymer dispersion comprising vinyl chloride, ethylene, and a copolymerizable functional monomer such as acrylamide is spray-dried in the presence of an anti-antagonist such as an inorganic extender pigment.
- an anti-antagonist such as an inorganic extender pigment.
- Patent Document 3 a slurry containing polymer particles made of a monomer mixture containing a monofunctional monomer and a polyfunctional monomer, a surfactant, an inorganic powder, and an aqueous medium is sprayed. A polymer particle aggregate obtained by drying is described.
- the fine particle assembly described in Patent Document 1 is described as “cross-linked polymer fine particles are interconnected”, “causes fusion between particles”, and the like. It is considered that the dispersibility is poor and the crosslinked polymer fine particles are fused.
- One of the purposes of the invention of Patent Document 1 is “providing a high-strength fine particle aggregate”, and the cross-linked polymer fine particles as a raw material are not fused and easily dispersed into primary particles. It is considered to be a feature and has a different purpose from the present invention. For this reason, it is difficult to pulverize the fine particle aggregate described in Patent Document 1 into clean primary particles even if it is intended to be primary particles by, for example, pulverization.
- the powder composition described in Patent Document 2 it is considered that fusion between the polymer powders is likely to occur during spray drying because the polymer powder constituting the powder composition does not have a crosslinked structure. Therefore, when the powder composition described in Patent Document 2 is also used as a compounding agent such as a light diffusing agent and a matting agent for paint, it is difficult to disperse to primary particles or a state close thereto, and the desired light diffusibility, gloss There was a problem that characteristics such as erasability could not be obtained.
- a compounding agent such as a light diffusing agent and a matting agent for paint
- the polymer particle assembly described in Patent Document 3 has no fusion between the polymer particles, but is 1 part by mass or more with respect to a total of 100 parts by mass of the monofunctional monomer and the polyfunctional monomer. Since the inorganic powder was included, there was a problem that the light transmittance was not good.
- the present invention has been made in view of the above-described conventional problems, and one of its purposes is to provide a resin particle aggregate that is easily dispersed in primary particles or a state close thereto and has good light transmittance. There is to do.
- Another object of the present invention is to provide a light diffusing resin composition and an optical film having a good light diffusibility and a light transmissive property, a good light diffusibility and a light transmissive property, or a good matte property. It is an object of the present invention to provide a coating composition having a coating composition, and an external preparation having a good soft focus effect (an effect of making wrinkles less noticeable) and light transmittance, or having a good matting property.
- a polymer particle aggregate is obtained by spray drying a slurry having a relatively low solid content concentration of about 20% by mass. Therefore, since the amount of water evaporated by spray drying is large, the time required for spray drying is long and the production efficiency is not good. Moreover, according to the manufacturing method of the Example of patent document 3, since the solid content concentration of the slurry used for spray drying is low, in one droplet at the time of spray drying, the ratio of resin particles is small and the ratio of water is Many. During spray drying, the droplets are considered to be dried in their size and become resin particle aggregates.
- the quantity of the resin particle contained in one resin particle aggregate is small, and the ratio of the space
- the resin particle aggregate obtained by the manufacturing method according to the example of Patent Document 3 is easily deformed and is likely to have a shape different from a spherical shape, so that it is difficult to handle.
- Comparative Example 6 of Patent Document 3 it is described that when inorganic particles were not used, aggregation was observed during polymerization, and a polymer particle aggregate could not be produced. . That is, in the method for producing a polymer particle assembly described in Patent Document 3, inorganic particles are required, and a resin particle assembly with good light transmittance cannot be produced.
- Still another object of the present invention is to efficiently produce a resin particle aggregate that is easy to handle, and to obtain a resin particle aggregate without using an amount of an inorganic component that affects light transmittance. It is to provide a manufacturing method.
- the resin particle aggregate of the present invention is a resin particle aggregate formed by aggregating a plurality of resin particles made of a polymer of a vinyl monomer, 100 parts by mass of particles and 1 to 5 parts by mass of a surfactant, and the resin particles are crosslinked with 9 to 50% by mass of a crosslinkable monomer based on the total mass of the resin particles, Particles contained in a dispersion in which the resin particle aggregate is dispersed in water with respect to the volume average particle diameter D1 of the resin particles, wherein the content of the inorganic component in the resin particle aggregate is 0.5% by mass or less.
- the volume average particle diameter D2 ratio D2 / D1 is 15 or less, and the volume average particle diameter D2 is a mixture of 0.50 g of the resin particle aggregate and 50 g of water, and the output is 400 W and the frequency is 20 kHz.
- a laser diffraction scattering method particle size distribution measuring device that calculates the volume average particle diameter of the particles using an optical model that matches the refractive index of the resin particles. The particle diameter is measured by a measuring method for measuring the volume average particle diameter of the particles contained in the dispersion.
- distributed the said resin particle aggregate to water with respect to the volume average particle diameter D1 of the said resin particle is 15 or less. Therefore, the resin particle aggregate has a property of being easily dispersed into primary particles or a state close thereto when dispersed in water. This is because when the resin particle aggregate is mixed with other components as a compounding agent such as a light diffusing agent or a matting agent for paint, the resin particle aggregate is easily dispersed to a primary particle or a state close thereto. Is shown.
- the volume average particle diameter D2 is the volume average particle of the resin particle aggregate.
- the value is approximately the same as the diameter and larger than 15 (for example, about 28 to 32).
- the resin particle aggregate having the above-described configuration contains 1 to 5 parts by mass of a surfactant with respect to 100 parts by mass of the resin particles, fusion between the resin particles can be suppressed.
- the resin particles are hard because they are crosslinked with 9 to 50% by mass of a crosslinkable monomer with respect to the total mass of the resin particles. As a result, the occurrence of fusion between the resin particles during production of the resin particle aggregate is suppressed.
- the resin particle aggregate having the above-described structure has good light transmittance since the content of the inorganic component is 0.5% by mass or less.
- the method for producing a resin particle aggregate of the present invention absorbs the second vinyl monomer in seed particles made of a polymer of the first vinyl monomer, A seed polymerization step of obtaining resin particles by a seed polymerization method for polymerizing a vinyl monomer of No. 2, a slurry containing 100 parts by mass of the obtained resin particles, 1 to 5 parts by mass of a surfactant, and an aqueous medium.
- the temperature of the slurry inlet is in the range of 80 ° C. to 220 ° C. by a spray dryer having a slurry inlet through which the slurry is sprayed and a powder outlet through which the resin particle aggregate is discharged.
- the ratio of the resin particles is large and the ratio of water is small in one droplet (sprayed slurry) at the time of spray drying. .
- the droplets are dried as they are (with moisture and the like removed) to form resin particle aggregates. Therefore, according to the said method, the quantity of the resin particle contained in one resin particle aggregate increases (filling rate is high), and the ratio of the space
- the second vinyl monomer contains 9 to 50% by mass of a crosslinkable monomer with respect to 100% by mass of the resin particles, and the solid content concentration of the slurry Is in the range of 24 to 40% by mass, so that polymerization can be performed without using inorganic particles in an amount exceeding 0.5 parts by mass with respect to 100 parts by mass of the resin particle aggregate that affects the light transmittance. It is possible to avoid agglomeration of the resin particles and the resin particles cannot be obtained, and a resin particle aggregate can be produced. Accordingly, it is possible to produce a resin particle aggregate having good light transmittance.
- the method of the present invention it is possible to efficiently produce an easy-to-handle resin particle aggregate, and the resin particle aggregate can be obtained without using an inorganic component in an amount that affects light transmittance. Obtainable.
- the resin particles since the resin particles contain 1 to 5 parts by mass of a surfactant with respect to 100 parts by mass of the resin particles, it is possible to prevent the resin particles from fusing together during spray drying. be able to. According to the method, the resin particles are hard because they are crosslinked with 9 to 50% by mass of a crosslinkable monomer with respect to the total mass of the resin particles. As a result, it is possible to prevent the resin particles from fusing together during spray drying. Further, according to the above method, since the water-soluble polymer is not used when the second vinyl monomer is polymerized, it is avoided that the water-soluble polymer connects the resin particles during spray drying. it can.
- the resin particles are melted. Wearing can be suppressed. Therefore, according to the method of the present invention, a resin particle aggregate in which fusion of resin particles is suppressed can be obtained.
- the light diffusing resin composition of the present invention is characterized by mixing a transparent base resin and the resin particle aggregate of the present invention in order to solve the above-mentioned problems.
- the resin particle aggregate is dispersed as primary particles or a state close to the primary particle aggregate. It can improve and can suppress the fall of light transmittance.
- the coating composition of the present invention is characterized by blending the resin particle aggregate of the present invention in order to solve the above problems.
- the resin particle aggregate of the present invention is mixed, the resin particle aggregate is dispersed as primary particles or a state close thereto, and in the case of a transparent coating composition Has good light diffusibility and light transmittance, and has a good matting property in the case of an opaque coating composition such as a paint.
- the optical film of the present invention is obtained by coating the coating composition on a substrate film in order to solve the above-mentioned problems. Thereby, the optical film which has favorable light diffusibility and light transmittance is realizable.
- the external preparation of the present invention is characterized by blending the resin particle aggregate of the present invention in order to solve the above-mentioned problems.
- the resin particle aggregate of the present invention is dispersed in a state of being close to or close to primary particles, which is favorable in the case of a transparent external preparation. It has a soft focus effect and light transmission, and has a good matte property in the case of an opaque external preparation.
- an easy-to-handle resin particle aggregate can be efficiently produced, and a resin particle aggregate suitable for producing a resin particle aggregate with a low content of inorganic components Manufacturing method, light diffusing resin composition having good light diffusibility and light transmittance, optical film having good light diffusibility and light transmittance, good light diffusibility and light transmittance, or It is possible to provide a coating composition having a good matting property, and an external preparation having a good soft focus effect (which makes wrinkles inconspicuous) and light transmittance, or a good matting property.
- the resin particle aggregate of the present invention is a resin particle aggregate formed by aggregating (aggregating) a plurality of resin particles (primary particles) made of a polymer of a vinyl monomer, and the resin particle 100
- the resin particles are crosslinked with 9 to 50% by mass of a crosslinkable monomer with respect to the total mass of the resin particles, and the resin particles include 1 part by mass and 1 to 5 parts by mass of a surfactant.
- the volume of particles contained in a dispersion in which the resin particle aggregate is dispersed in water with respect to the volume average particle diameter D1 of the resin particles, the content of the inorganic component in the aggregate is 0.5% by mass or less.
- the volume average particle diameter D2 is obtained by mixing 0.50 g of the resin particle aggregate and 50 g of water, and irradiating the mixture with ultrasonic waves for 10 minutes using an ultrasonic disperser with an output of 400 W and a frequency of 20 kHz.
- particle size distribution measuring device After obtaining a dispersion by using a laser diffraction scattering method particle size distribution measuring device that calculates the volume average particle diameter of the particles using an optical model that matches the refractive index of the resin particles, included in the dispersion Measured by a measuring method for measuring the volume average particle diameter of the particles to be measured.
- the ratio D2 / D1 is more preferably 11 or less.
- the resin particle aggregate of the present invention is a particle having a particle diameter larger than the volume average particle diameter D3 of the resin particle aggregate in the particles contained in a dispersion in which the resin particle aggregate is dispersed in water.
- the ratio is preferably 1% by volume or less.
- 99% by volume or more is provided with a property of being dispersed in particles having a smaller particle diameter. This is because when the resin particle aggregate is mixed with other components as a compounding agent such as a light diffusing agent or a matting agent for paint, the resin particle aggregate is easily dispersed to a primary particle or a state close thereto. Is shown. Therefore, in this case, it is possible to realize a resin particle aggregate that is more easily dispersed into primary particles or a state close thereto.
- the ratio of the particles having a particle diameter larger than the volume average particle diameter D3 of the resin particle aggregate in the particles contained in the dispersion in which the resin particle aggregate is dispersed in water is the resin particle aggregate.
- the volume average particle diameter D3 of the resin particle aggregate was measured by the arithmetic average volume average particle diameter measured by the laser diffraction scattering method, specifically, by the measurement method described in the section of [Example]. It shall refer to the value.
- the vinyl monomer is composed of a monofunctional vinyl monomer and the crosslinkable monomer.
- the monofunctional vinyl monomer used in the present invention is a compound having one polymerizable alkenyl group (in a broad sense) in one molecule.
- the monofunctional vinyl monomer include aromatic vinyl monomers; (meth) acrylic acid ester monomers, vinyl halide monomers, vinyl cyanide monomers, and the like.
- the aromatic vinyl monomer that can be used include styrenes (styrene monomers) such as styrene and ⁇ -methylstyrene.
- Examples of the (meth) acrylate monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth) Alkyl (meth) acrylates such as isobutyl acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, and n-hexyl (meth) acrylate can be used.
- These monofunctional vinyl monomers may be used alone or in combination of two or more.
- At least one monomer selected from styrenes and alkyl (meth) acrylates is preferred, and styrene and alkyl groups are preferred. More preferred is at least one monomer selected from alkyl (meth) acrylates having 1 to 4 carbon atoms.
- the monofunctional vinyl-based monomer is an alkyl (meth) acrylate having an alkyl group with 5 or more carbon atoms, the resin particles are liable to be fused and become difficult to become primary particles.
- “(meth) acryl” means acryl or methacryl
- (meth) acrylate” means acrylate or methacrylate.
- the crosslinkable monomer that crosslinks the resin particles is a compound having a plurality of polymerizable alkenyl groups (broadly defined vinyl groups) in one molecule.
- the crosslinkable monomer include styrene-based crosslinkable monomers such as divinylbenzene; (meth) acrylic acid ester-based crosslinkable properties such as ethylene glycol di (meth) acrylate and trimethylolpropane tri (meth) acrylate. And monomers.
- the crosslinkable monomer is preferably at least one monomer of divinylbenzene, ethylene glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate.
- the amount of the crosslinkable monomer that crosslinks the resin particles is the total mass of the resin particles (the mass of the monofunctional vinyl monomer, the mass of the crosslinkable monomer, and the mass of the polymerization initiator). And 9 to 50% by mass based on the total of the mass of additives (chain transfer agent etc.) involved in the polymerization reaction used as necessary and the mass of seed particles used as needed) Is within the range.
- the amount of the crosslinkable monomer is less than 9% by mass with respect to the total mass of the resin particles, the resin particles become soft when heated, so that the resin particles when drying the resin particles for producing the resin particles The two are fused.
- the amount of the crosslinkable monomer exceeds 50% by mass with respect to the total mass of the resin particles, the resin particles aggregate at the time of polymerization for producing the resin particles, and a desired resin particle aggregate is obtained. It becomes impossible.
- the amount of the crosslinkable monomer is more preferably 20 to 50% by mass with respect to the total mass of the resin particles. Thereby, fusion of resin particles at the time of drying and aggregation of the resin particles at the time of polymerization can be further suppressed.
- the surfactant constituting the resin particle aggregate of the present invention is not particularly limited, and includes an anionic surfactant, a nonionic surfactant, a cationic surfactant, and a zwitterionic surfactant. Either can be used.
- anionic surfactant examples include dialkyl sulfosuccinates such as sodium dioctyl sulfosuccinate; phosphate esters such as sodium polyoxyethylene alkylphenyl ether phosphate and sodium polyoxyalkylene aryl ether phosphate; sodium oleate Fatty acid oils such as castor oil potash; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; alkyl benzene sulfonates such as sodium dodecylbenzene sulfonate; alkyl naphthalene sulfonates; alkane sulfonates; Naphthalene sulfonic acid formalin condensate; polyoxyethylene alkyl phenyl ether sulfate salt; polyoxyethylene alkyl sulfate ester salt and the like.
- dialkyl sulfosuccinates such as sodium dio
- nonionic surfactant examples include polyoxyethylene alkyl ethers such as polyoxyethylene tridecyl ether, polyoxyethylene alkyl phenyl ethers, polyoxyethylene styrenated phenyl ethers, and alkylene groups having 3 or more carbon atoms.
- Polyoxyalkylene alkyl ether such as polyoxyalkylene tridecyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester such as polyoxyethylene sorbitan monolaurate, polyoxyethylene alkylamine, glycerin fatty acid ester, oxy And ethylene-oxypropylene block copolymer.
- cationic surfactant examples include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride.
- zwitterionic surfactant examples include lauryl dimethylamine oxide and phosphate ester or phosphite ester surfactants.
- the surfactant constituting the resin particle aggregate of the present invention it is preferable to use at least one of an anionic surfactant and a nonionic surfactant among these surfactants.
- an anionic surfactant and a nonionic surfactant among these surfactants.
- phosphoric acid ester salts and sulfosuccinates are preferable as the anionic surfactant
- polyoxyethylene alkyl phenyl ether and polyoxyethylene styrenated phenyl ether are preferable as the nonionic surfactant.
- the said surfactant may be used independently and may be used in combination of 2 or more type.
- the content of the surfactant is in the range of 1 to 5 parts by mass with respect to 100 parts by mass of the resin particles. If the content of the surfactant is less than 1 part by mass with respect to 100 parts by mass of the resin particles, the effect of suppressing the fusion of the resin particles becomes insufficient, such being undesirable. When the content of the surfactant exceeds 5 parts by mass with respect to 100 parts by mass of the resin particles, an effect commensurate with the amount of the surfactant cannot be obtained.
- the content of the inorganic component in the resin particle aggregate of the present invention is more preferably substantially 0 (less than the detection limit), but is acceptable if it is 0.5% by mass or less.
- the inorganic component include inorganic powders such as barium sulfate, titanium oxide, calcium carbonate and colloidal silica; sparingly water-soluble inorganic salts such as calcium triphosphate, magnesium hydroxide, magnesium pyrophosphate, barium sulfate, calcium carbonate and silica Etc.
- the polymerization method for obtaining the resin particles constituting the resin particle aggregate of the present invention is not particularly limited, and methods such as an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, and a seed polymerization method can be used. .
- methods other than the suspension polymerization method in which the particle size distribution is generally wide are preferable, and preferable volume average particle size (0.1 to 2.0 ⁇ m) and preferable particle size distribution (variation coefficient 20% or less) are obtained.
- the seed polymerization method is most preferable because it is possible to easily obtain resin particles crosslinked with 9 to 50% by mass of a crosslinkable monomer with respect to the total mass of the resin particles.
- seed particles made of a polymer of a first vinyl monomer are allowed to absorb the second vinyl monomer and polymerize the second vinyl monomer.
- the seed particles are not particularly limited, but are preferably (meth) acrylic resin particles.
- the seed particles are more preferably non-crosslinked.
- polymerization may be performed using a water-soluble polymer such as polyvinyl alcohol or polyvinylpyrrolidone as a dispersion stabilizer in order to improve the polymerization stability.
- a water-soluble polymer such as polyvinyl alcohol or polyvinylpyrrolidone
- the water-soluble polymer functions as a binder, and when the resin particles are spray-dried, the water-soluble polymer is fused with the resin particles to form a resin. Since the particles are connected to each other, it may not be possible to obtain an aggregate of resin particles that is easily dispersed in the intended primary particles or a state close thereto.
- the resin particles constituting the resin particle aggregate of the present invention are preferably produced by polymerization without using a water-soluble polymer.
- a polymerization method such as a suspension polymerization method using an inorganic dispersion stabilizer is not preferable because the inorganic dispersion stabilizer remains as it is in the resin particle aggregate, which may reduce the light transmittance of the resin particles.
- the mass average molecular weight (Mw) of the seed particles is preferably 50,000 or less. When the mass average molecular weight of the seed particles exceeds 50,000, the seed particles hardly absorb the second vinyl monomer, and the particle size distribution of the obtained resin particles is widened.
- the particle size distribution of the resin particles spreads, the number of contact points between the particles increases, so that fusion between the resin particles is likely to occur, and the resin particle aggregate is difficult to be dispersed in the primary particles or a state close thereto. Further, when the particle size distribution of the resin particles is widened, when the resin particle aggregate of the present invention is mixed with other components, characteristics such as light diffusibility and matting of the resin particles are likely to be non-uniform.
- the seed particles are preferably non-crosslinked particles or finely crosslinked particles (particles crosslinked to such an extent that they can be dissolved in a solvent).
- the seed particles are cross-linked so as not to dissolve in the solvent, the amount of vinyl monomer absorbed by the seed particles is reduced, and further, the resin particles become a core-shell shape (the seed particles keep a spherical shape). It is not preferable for obtaining spherical particles with uniform inside of the particles such as deformation of the particles.
- the ratio of the seed particles to the total mass of the vinyl monomer constituting the resin particles is preferably 10% by mass or less.
- the ratio of the seed particles to the total mass of the resin particles exceeds 10% by mass, the seed particles having a low glass transition temperature are melted when the resin particles are dried, and the resin particles Since it becomes a factor which fuses each other, it is not preferable.
- the ratio of the seed particles with respect to the total mass of the resin particles can be analyzed by dissolving the seed particles in the resin particles with a solvent.
- the volume average particle diameter D1 of the resin particles constituting the resin particle aggregate of the present invention is preferably in the range of 0.1 to 2.0 ⁇ m, and preferably in the range of 0.3 to 1.5 ⁇ m. More preferably, it is in the range of 0.5 to 1.0 ⁇ m.
- the volume average particle diameter D1 of the resin particles is less than 0.1 ⁇ m, characteristics such as light transmittance may be deteriorated.
- the volume average particle diameter D1 of the resin particles is larger than 2.0 ⁇ m, a large amount of resin particles are gathered in order to reduce the light diffusibility and matte characteristics or to obtain the desired light diffusibility and matte characteristics. It may be necessary to use the body.
- the coefficient of variation of the particle diameter of the resin particles constituting the resin particle aggregate of the present invention is preferably 20% or less. More preferably, the resin particles have a volume average particle diameter D1 in the range of 0.1 to 2.0 ⁇ m and a coefficient of variation of the particle diameter of 20% or less.
- the properties such as light diffusibility and matting of the resin particles become uniform.
- grains contact is wide, it becomes difficult to produce the fusion
- the coefficient of variation refers to a coefficient of variation of the volume-based particle size distribution, specifically a value measured by the measurement method described in the section of [Example].
- the production method of the present invention comprises a seed polymerization method in which a second vinyl monomer is absorbed into seed particles composed of a polymer of the first vinyl monomer, and the second vinyl monomer is polymerized.
- Seed polymerization step for obtaining resin particles, 100 parts by mass of the obtained resin particles, 1 to 5 parts by mass of a surfactant, and a slurry inlet into which the slurry is introduced by spraying the slurry and the slurry Spraying is performed with a spray dryer having a powder outlet through which resin particle aggregates are discharged under conditions where the slurry inlet temperature is in the range of 80 ° C to 220 ° C and the powder outlet temperature is in the range of 40 ° C to 100 ° C.
- a spray drying step of drying, and at the time of polymerization of the second vinyl monomer, no water-soluble polymer is used, and the resin particles are 9 to 50% by mass with respect to 100% by mass of the resin particles.
- a slurry of Solid concentration is in the range of 24-40 wt%.
- the first vinyl monomer and the second vinyl monomer the above-described vinyl monomers can be used, and the first vinyl monomer is not limited to the crosslinkable monomer.
- the second vinyl monomer is composed of the monofunctional vinyl monomer and the crosslinkable monomer, while not including a monomer and consisting of only the monofunctional vinyl monomer. It is preferable.
- the first vinyl monomer is preferably the (meth) acrylic acid ester monomer or the aromatic vinyl monomer, more preferably the alkyl (meth) acrylate or styrene, More preferably, it is an alkyl (meth) acrylate having 1 to 4 carbon atoms.
- Both the surfactant and the aqueous medium may be added after the polymerization of the second vinyl monomer, or may be added before the polymerization of the second vinyl monomer. It is preferable to add it before the polymerization of the vinyl monomer. Therefore, it is preferable to disperse and polymerize the second vinyl monomer in an aqueous medium containing a surfactant, and use the reaction liquid after polymerization in the spray drying process without removing water. Thereby, a resin particle aggregate can be manufactured efficiently.
- the aqueous medium is not particularly limited, and examples thereof include water and a mixed medium of water and a water-soluble organic medium (lower alcohol (alcohol having 5 or less carbon atoms) such as methanol and ethanol).
- the amount of the aqueous medium used is usually in the range of 100 to 1000 parts by mass with respect to 100 parts by mass of the second vinyl monomer in order to stabilize the resin particles.
- the polymerization of the second vinyl monomer in the aqueous medium is preferably performed by stirring an aqueous suspension in which the second vinyl monomer is dispersed as spherical droplets.
- the stirring may be performed loosely enough to prevent, for example, floating of spherical droplets and sedimentation of particles after polymerization.
- the polymerization temperature of the second vinyl monomer is preferably in the range of 30 to 100 ° C., and more preferably in the range of 40 to 80 ° C.
- the time for maintaining this polymerization temperature is preferably within the range of 0.1 to 20 hours.
- a polymerization initiator In the polymerization of the second vinyl monomer, a polymerization initiator is usually used.
- the polymerization initiator include peroxides such as benzoyl peroxide, lauroyl peroxide, tert-butylperoxyisobutyrate; 2,2′-azobisisobutyronitrile, 2,2′-azobis (2 , 4-dimethylvaleronitrile), 2,2′-azobis (2-methylpropionate) and the like; and peroxy salts such as potassium persulfate and ammonium persulfate.
- the polymerization initiator used for the polymerization of the second vinyl monomer is an oil such as benzoyl peroxide or 2,2′-azobisisobutyronitrile when the surfactant concentration is higher than the critical micelle concentration. It is preferable to use a soluble polymerization initiator.
- an oil-soluble polymerization initiator when an oil-soluble polymerization initiator is used, new particles other than the intended resin particles are used compared to the case where a water-soluble polymerization initiator such as potassium persulfate is used. Can be prevented from occurring.
- the amount of the polymerization initiator used is preferably in the range of 0.01 to 10 parts by weight, and in the range of 0.01 to 5 parts by weight, with respect to 100 parts by weight of the second vinyl monomer. More preferably.
- the usage-amount of a polymerization initiator is less than 0.01 mass part with respect to 100 mass parts of 2nd vinylic monomers, it is difficult for a polymerization initiator to fulfill
- the amount of the surfactant used in the polymerization of the second vinyl monomer ranges from 1 to 5% by mass with respect to the total amount of the first vinyl monomer and the second vinyl monomer. Is within.
- the amount of the surfactant used is less than 1% by mass with respect to the total amount of the first vinyl monomer and the second vinyl monomer, it is difficult to maintain the polymerization stability. It is not preferable.
- the amount of the surfactant used exceeds 5% by mass with respect to the total amount of the first vinyl monomer and the second vinyl monomer, new particles other than the intended resin particles Since it occurs and the function as a light-diffusion agent etc. falls, it is not preferable.
- a chain transfer agent may be added to the polymerization of the second vinyl monomer in order to improve the heat resistance of the resin particles.
- the chain transfer agent include mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan and tert-dodecyl mercaptan; terpenes such as ⁇ -terpinene and dipentene; halogenated hydrocarbons such as chloroform and carbon tetrachloride; Examples include ⁇ -methylstyrene dimer.
- an additive such as an antioxidant can be added.
- the seed particles are obtained by polymerizing the first vinyl monomer.
- the polymerization method of the first vinyl monomer is not particularly limited, but is a soap-free polymerization method (emulsion polymerization method not using a surfactant), emulsion polymerization method, suspension polymerization method, dispersion polymerization method, seed weight. Methods such as legal methods can be used. Among these polymerization methods, the soap-free polymerization method is most preferable.
- the polymerization temperature of the first vinyl monomer is preferably in the range of 30 to 100 ° C., and more preferably in the range of 40 to 80 ° C.
- the time for maintaining this temperature is preferably in the range of 1 to 30 hours.
- a polymerization initiator is usually used.
- the same polymerization initiator as that used for the second vinyl monomer can be used, but potassium persulfate, ammonium persulfate, etc.
- the water-soluble polymerization initiator is preferably used.
- the amount of the polymerization initiator used is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the first vinyl monomer, and 0.01 to 5 parts by mass. More preferably within the range.
- the usage-amount of the said polymerization initiator is less than 0.01 mass part with respect to 100 mass parts of 1st vinylic monomers, it is difficult for the said polymerization initiator to fulfill
- a chain transfer agent can be added to the polymerization of the first vinyl monomer in order to adjust the molecular weight.
- the chain transfer agent those used for the polymerization of the second vinyl monomer can be used.
- a resin particle aggregate is formed from the resin particles, and the particle diameter and shape of the resin particle aggregate can also be controlled.
- the spray drying method generally uses a spray dryer such as a spray dryer or an air dryer, and sprays an aqueous dispersion (slurry containing resin particles) together with a gas air stream to dry the particles. It is possible to adjust the particle diameter, particle shape, and the like of the resin particle aggregate by appropriately adjusting the water dispersion supply speed, the drying temperature, the atomizer rotation speed of the spray dryer, and the like in spray drying.
- the drying temperature is such that the temperature of the slurry inlet into which the slurry is sprayed is in the range of 80 ° C. to 220 ° C., and the temperature of the powder outlet from which the resin particle aggregate is discharged is in the range of 40 ° C. to 100 ° C. .
- the temperature at the slurry inlet is higher than 220 ° C., the resin particles are likely to be fused with each other, and a resin particle aggregate in which the resin particles are connected to each other is obtained.
- the temperature at the slurry inlet is lower than 80 ° C., drying tends to be insufficient, and problems such as excessively low drying efficiency occur.
- the powder outlet temperature is lower than 40 ° C.
- drying may be insufficient.
- the temperature at the powder outlet is higher than 100 ° C., there arises a problem that the resin particles are easily fused.
- the solid content concentration in the slurry used for spray drying that is, the concentration of the resin particles in the slurry (resin particle dispersion) used for spray drying is preferably 24% by mass or more and 40% by mass or less.
- the solid content concentration in the slurry is lower than 24% by mass, the amount of the aqueous medium increases, so that the resin particle aggregate is easily deformed during drying.
- the solid content concentration in the slurry is lower than 24% by mass, since the ratio of voids in the resin particle aggregate increases, the resin particle aggregate easily deforms and tends to have a shape different from a spherical shape. Hateful.
- the solid content concentration in the slurry is higher than 40% by mass, the production becomes difficult.
- the resin particles may be classified after the seed polymerization step, and the classified resin particles may be used in the spray drying step. Thereby, since the coarse particle contained in a slurry can be reduced, the coarse particle contained in a resin particle aggregate can be reduced. As a result, when the coating composition comprising the resin particle aggregate is coated, streaks occur in the (cured) coating composition, or the coating composition comprising the resin particle aggregate is blended. When coated on the base film, it is possible to prevent bright spots from occurring in the optical film obtained after coating.
- the content of the inorganic component in the slurry used in the spray drying step is preferably 0.5% by mass or less with respect to the total mass of the resin particles.
- the volume average particle diameter of the resin particle aggregate of the present invention is preferably in the range of 2 to 250 ⁇ m, and more preferably in the range of 5 to 100 ⁇ m.
- a resin particle aggregate having a volume average particle diameter of less than 2 ⁇ m is difficult to manufacture.
- the drying efficiency will become low when the volume average particle diameter of a resin particle aggregate exceeds 250 micrometers, manufacturing efficiency will become low.
- the light diffusing resin composition of the present invention is obtained by mixing a transparent base resin and the resin particle aggregate of the present invention as a light diffusing agent.
- the transparent base resin constituting the light diffusing resin composition of the present invention a highly transparent thermoplastic resin is usually used.
- the transparent base resin include (meth) acrylic resins (poly (meth) acrylic acid esters) such as polymethyl methacrylate, alkyl (meth) acrylate-styrene copolymers, polycarbonate, polyester, polyethylene, and polypropylene.
- thermoplastic resins such as polystyrene.
- thermoplastic resins when excellent transparency is required, (meth) acrylic resin, alkyl (meth) acrylate-styrene copolymer, polycarbonate, polyester, and polystyrene are preferred.
- These thermoplastic resins may be used alone or in combination of two or more.
- the addition ratio of the resin particle aggregate to the transparent base resin is preferably in the range of 0.01 to 100 parts by mass with respect to 100 parts by mass of the transparent base resin. Thereby, light diffusibility and light transmittance can be made favorable. When the resin particle aggregate is less than 0.01 part by mass, it may be difficult to impart light diffusibility. When the resin particle aggregate is more than 100 parts by mass, light diffusibility can be obtained, but light transmittance may be lowered.
- a more preferable addition ratio of the resin particle aggregate is in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the transparent base resin.
- the production method of the light diffusing resin composition is not particularly limited, for example, by mixing the resin particle aggregate of the present invention and the transparent base resin by a mixing method such as a mechanical pulverization mixing method, A light diffusing resin composition can be produced.
- a mixing method such as a mechanical pulverization mixing method
- mixing and stirring can be performed using, for example, a Henschel mixer, a V-type mixer, a turbula mixer, a hybridizer, a rocking mixer, and the like.
- a molded body (light diffusing member) made of the light diffusing resin composition can be produced by molding the light diffusing resin composition.
- the resin particle aggregate and the transparent base resin are mixed with a mixer and kneaded with a melt kneader such as an extruder to obtain a pellet made of a light diffusing resin composition, and then the pellet is extruded.
- a molded body having an arbitrary shape made of the light diffusing resin composition can be obtained.
- the molded body made of the light diffusing resin composition can be used as, for example, an illumination cover for a light emitting diode (LED) illumination, an illumination cover for a fluorescent lamp illumination, a light diffusion plate of a light diffusion plate for a liquid crystal display device, or the like.
- the configuration of the liquid crystal display device in which the light diffusing plate is used is not particularly limited as long as it includes the light diffusing plate.
- the liquid crystal display device includes at least a liquid crystal display panel having a display surface and a back surface, a light guide plate disposed on the back surface side of the panel, and a light source that makes light incident on the side surface of the light guide plate.
- the liquid crystal display device includes a light diffusing plate on a surface of the light guide plate facing the liquid crystal display panel, and a reflection sheet on the opposite surface side of the surface of the light guide plate facing the liquid crystal display panel.
- This arrangement of light sources is generally referred to as an edge light type backlight arrangement.
- As an arrangement of the light sources in the liquid crystal display device there is a direct type backlight arrangement in addition to the edge light type backlight arrangement.
- this arrangement is an arrangement in which a light source is arranged on the back side of the liquid crystal display panel and at least a light diffusing plate arranged between the liquid crystal display panel and the light source.
- the resin particle aggregate of the present invention can be contained in a coating composition as a matting agent for paint, a light diffusing agent for light diffusing film, an antiglare film particle, or the like.
- the coating composition of the present invention is obtained by blending the resin particle aggregate of the present invention with other components.
- the coating composition contains a binder resin as necessary.
- a binder resin an organic solvent, a water-soluble resin, or an emulsion-type aqueous resin that can be dispersed in water can be used.
- binder resins include acrylic resins, alkyd resins, polyester resins, polyurethane resins, chlorinated polyolefin resins, and amorphous polyolefin resins. These binder resins can be appropriately selected depending on the adhesion to the substrate to be coated, the environment in which they are used, and the like.
- the addition amount of the binder resin and the resin particle aggregate varies depending on the use, the thickness of the coating film to be formed, the average particle diameter of the resin particles, and the coating method.
- the coating composition contains a solvent as necessary. Although it does not specifically limit as a solvent which comprises the composition for coating, It is preferable to use the solvent which can melt
- hydrocarbon solvents such as toluene and xylene
- ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone
- ester solvents such as ethyl acetate and n-butyl acetate Ether solvents such as dioxane, ethylene glycol diethyl ether and ethylene glycol mono n-butyl ether can be used as the solvent.
- an aqueous solvent such as water or alcohol
- these solvents may be used alone or in combination of two or more.
- the solvent content in the coating composition is usually in the range of 20 to 60% by mass relative to the total amount of the coating composition.
- the coating composition may be a known coating surface adjusting agent, fluidity adjusting agent, ultraviolet absorber, light stabilizer, curing catalyst, extender pigment, colored pigment, metal pigment, mica powder pigment, dye, organic, if necessary. It may contain a solvent or the like.
- the formation method of the coating film using the coating composition is not particularly limited, and any known method can be used.
- Examples of the method for forming a coating film using the coating composition include a spray coating method, a roll coating method, a gravure coating method, a comma coating method, and a brush coating method.
- the coating composition may be diluted with a diluent to adjust the viscosity as necessary.
- Diluents include hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as dioxane and ethylene glycol diethyl ether; water An alcohol solvent or the like.
- diluents may be used alone or in combination of two or more.
- optical film The optical film of the present invention is obtained by coating the base film with the coating composition of the present invention.
- the optical film of the present invention can be used as an antiglare film, a light diffusion film, or the like.
- the material of the base film is not particularly limited as long as it has transparency.
- polyester resin such as polyethylene terephthalate, triacetyl cellulose resin, polystyrene resin, polycarbonate resin, cycloolefin Based resins and the like.
- polyethylene terephthalate is particularly preferable from the viewpoint of surface smoothness and mechanical strength.
- the thickness of the base film is preferably in the range of 5 to 300 ⁇ m.
- the thickness of the base film is less than 5 ⁇ m, handling during coating, printing, and secondary processing becomes difficult, and workability may be reduced.
- the thickness of the base film is larger than 300 ⁇ m, the visible light transmittance of the base film itself may be lowered.
- the optical film of the present invention can be obtained by forming a layer of the coating composition of the present invention on at least one surface of a base film by means such as coating.
- the coating method include a roll coating method and a spray coating method.
- the resin particle aggregate of the present invention can also be used as a raw material for external preparations.
- the external preparation of the present invention is obtained by blending the resin particle aggregate of the present invention with other components.
- the content of the resin particle aggregate in the external preparation can be appropriately set according to the type of external preparation, but is preferably in the range of 1 to 80% by mass, and is preferably in the range of 5 to 70% by mass. More preferred.
- the content of the resin particle aggregate with respect to the total amount of the external preparation is less than 1% by mass, a clear effect due to the inclusion of the resin particle aggregate may not be recognized.
- the content of the resin particle aggregate exceeds 80% by mass, a remarkable effect commensurate with the increase in content may not be recognized, which is not preferable in terms of production cost.
- Examples of external preparations include cosmetics and external medicines.
- Cosmetics include, for example, pre-shave lotions, body lotions, lotions, creams, emulsions, body shampoos, antiperspirants, and other cosmetics; soaps, scrubs, and other cleaning cosmetics; packs; shavings Lipstick; Lipstick; Blusher; Eyebrow cosmetics; Manicure cosmetics; Hair wash cosmetics; Hair dyes; Hair dyes; Fragrances; Aromatic cosmetics; Toothpaste; Bath preparations; Sunscreen products; Cosmetics for body such as powder are listed.
- the external medicine is not particularly limited as long as it is applied to the skin, and examples thereof include pharmaceutical creams, ointments, pharmaceutical emulsions, and pharmaceutical lotions.
- a main agent or additive generally used can be blended according to the purpose within a range not impairing the effects of the present invention.
- main agents or additives include water, lower alcohols (alcohols having 5 or less carbon atoms), oils and fats, hydrocarbons, higher fatty acids (fatty acids having 12 or more carbon atoms), higher alcohols (having 6 or more carbon atoms).
- sterols fatty acid esters (cetyl 2-ethylhexanoate, etc.), metal soaps, moisturizers, surfactants (sorbitan sesquioleate, etc.), polymer compounds, clay minerals (extreme pigments, adsorbents, etc.)
- the mass average molecular weight of the seed particles was measured using gel permeation chromatography (GPC).
- the measured mass average molecular weight is a polystyrene (PS) conversion mass average molecular weight.
- the measuring method is as follows. First, 50 mg of a sample was dissolved in 10 ml of tetrahydrofuran (THF). The resulting solution was filtered using a 0.45 ⁇ m non-aqueous chromatographic disk. The obtained filtrate was analyzed by GPC, and PS-converted mass average molecular weight was measured.
- GPC measurement conditions were as follows.
- GPC apparatus trade name “Gel Permeation Chromatograph HLC-8020” manufactured by Tosoh Corporation Column: Two trade names “TSKgel GMH XL-L” (diameter 7.8 mm ⁇ length 30 cm) manufactured by Tosoh Corporation Column temperature: 40 ° C.
- Carrier gas Tetrahydrofuran (THF)
- Carrier gas flow rate 1 mL / min
- Injection / pump temperature 35 ° C
- Detection RI (differential refractive index detector)
- Injection volume 100 ⁇ L Standard polystyrene for calibration curve for calculating PS-converted mass average molecular weight: trade name “shodex” (mass average molecular weight: 1030000) manufactured by Showa Denko KK and standard polystyrene for calibration curve (mass average molecular weight: manufactured by Tosoh Corporation) 5480000, 3840000, 355000, 102000, 37900, 9100, 2630, 870) [Measurement method of volume average particle diameter of seed particles and resin particles, and coefficient of variation of resin particles]
- the volume average particle diameters of seed particles and resin particles were measured as follows.
- the volume average particle diameters of the seed particles and the resin particles were measured with a laser diffraction scattering particle size distribution measuring device “LS230” manufactured by Beckman Coulter, Inc. Specifically, 0.1 g of a measurement target particle (seed particle or resin particle) is taken in a test tube, 0.1% by mass nonionic surfactant (polyoxyethylene sorbitan monolaurate (ethylene oxide addition mole number 20), product) The name “Leodol TW-L120” (Kao Corporation)) 10 ml of aqueous solution is added to the particles to be measured, and the aqueous solution and the particles to be measured are added to a mag mixer (touch mixer) “MT-31” type manufactured by Yamato Scientific Co., Ltd.
- a mag mixer touch mixer
- test tube is put in a desktop ultrasonic cleaner “VS-150” manufactured by VervoCrea Co., Ltd., which is a commercially available ultrasonic cleaner, and ultrasonic waves are applied to the test tube with this ultrasonic cleaner.
- VS-150 a desktop ultrasonic cleaner manufactured by VervoCrea Co., Ltd.
- the volume average particle size of the particles to be measured contained in the obtained dispersion and the standard deviation of the volume-based particle size distribution were measured with a laser diffraction scattering particle size distribution measuring device “LS230” manufactured by Beckman Coulter, Inc.
- the measured value of the arithmetic average volume average particle size (the arithmetic average value of the volume-based particle size distribution) is displayed as the measured value of the volume average particle size. Therefore, here, the measured value of the volume average particle diameter of the arithmetic average of the measurement target particles is set as the measurement value of the volume average particle diameter of the measurement target particles.
- the coefficient of variation of the particle diameter of the measurement target particles was calculated by the following mathematical formula.
- Variation coefficient of particle diameter of measurement target particle (standard deviation of volume-based particle size distribution of measurement target particle ⁇ volume average particle diameter of measurement target particle) ⁇ 100
- This laser diffraction / scattering particle size distribution measuring device analyzes the spatial intensity distribution data of the diffracted / scattered light of the particle using an optical model that matches the refractive index of the particle to be measured, Since the particle size distribution is calculated, it is necessary to input the refractive index of the particles to be measured.
- an estimated value of the refractive index was input to the laser diffraction / scattering particle size distribution measuring apparatus as the refractive index of the measurement target particle used for the data analysis.
- the refractive index of the homopolymer of the vinyl monomer was used as an estimated value of the refractive index of the measurement target particle.
- an average value obtained by weighted average of the refractive index of each vinyl monomer homopolymer by the amount of each vinyl monomer used was used as an estimate of the refractive index of the particles to be measured.
- volume average particle diameter of the resin particle aggregate was measured as follows. That is, the volume average particle diameter of the resin particle aggregate was measured with a laser diffraction scattering particle size distribution measuring device “LS230” manufactured by Beckman Coulter, Inc.
- 0.1 g of particles seed particles or resin particles
- 0.1% by mass nonionic surfactant polyoxyethylene sorbitan monolaurate (ethylene oxide addition mole number 20), trade name “ "Rheodor TW-L120” (Kao Corporation)
- 10 ml of aqueous solution was added to the resin particle assembly, and the aqueous solution and the resin particle assembly were added to a mag mixer (touch mixer) "MT-31" type manufactured by Yamato Scientific Co., Ltd. Mixing for 2 seconds gave a mixture.
- the volume average particle diameter of the particles contained in the obtained mixed liquid was measured with a laser diffraction scattering particle size distribution measuring device “LS230” manufactured by Beckman Coulter Inc.
- the measured value of the arithmetic average volume average particle diameter is displayed as the measured value of the volume average particle diameter. Therefore, here, the measurement value of the arithmetic average volume average particle diameter of the resin particle aggregate is taken as the measurement value of the volume average particle diameter of the resin particle aggregate.
- the estimated value of the refractive index of the resin particle was input to the laser diffraction / scattering particle size distribution measuring device, and data analysis of the laser diffraction / scattering particle size distribution measuring device was performed using an optical model matched to the refractive index of the resin particle. As described above, the estimated value of the refractive index of the resin particles was calculated from the refractive index of the vinyl monomer homopolymer.
- resin particle aggregates with respect to the volume average particle diameter D1 of the resin particles are used as two kinds of evaluation values for evaluating the dispersibility of the resin particle aggregates to primary particles or a state close thereto.
- the ratio D2 / D1 of the volume average particle diameter D2 of particles contained in a dispersion in which the body is dispersed in water hereinafter referred to as “resin particle assembly dispersion”
- the ratio of particles having a particle diameter larger than the volume average particle diameter D3 of the resin particle aggregate in the particles to be measured was measured as follows.
- the volume average particle diameter D2 and the volume-based particle size distribution of the particles contained in the resin particle assembly dispersion obtained here were measured with a laser diffraction scattering particle size distribution measuring device “LS230” manufactured by Beckman Coulter, Inc. .
- the estimated value of the refractive index of the resin particle was input into the laser diffraction / scattering particle size distribution measuring device, and data analysis of the laser diffraction / scattering particle size distribution measuring device was performed using an optical model matched to the refractive index of the resin particle.
- the estimated value of the refractive index of the resin particles was calculated from the refractive index of the vinyl monomer homopolymer.
- the volume average of the resin particles The ratio D2 / D1 of the volume average particle diameter D2 of the particles contained in the resin particle assembly dispersion with respect to the particle diameter D1 was calculated.
- the resin particle aggregate The ratio of particles having a particle diameter larger than the volume average particle diameter D3 of the resin particle aggregate in the particles contained in the body dispersion liquid (hereinafter also referred to as “dispersibility evaluation value”) was calculated.
- the ratio (D2 / D1) is 15 or less, the resin particle aggregate can be evaluated as having good dispersibility in the primary particles or a state close thereto. Even when the content is 1% by volume or less, it can be evaluated that the dispersibility into primary particles or a state close thereto is good.
- the total light transmittance of the molded product was measured using a haze meter “NDH 2000” manufactured by Nippon Denshoku Industries Co., Ltd. using JIS K7361 (total light transmittance of plastic-transparent material). Test method-Part 1: Single beam method). Further, in the following examples and comparative examples, the haze of the molded product was determined using JIS K7136-1 (plastic-transparent material haze method) using a haze meter “NDH 2000” manufactured by Nippon Denshoku Industries Co., Ltd. ).
- the measurement is performed using NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd.
- the haze of the molded body is 99% or more, the molded body has high light diffusibility, so when the molded body is incorporated in a liquid crystal backlight unit, when the molded body is attached to a lighting fixture as a lighting cover, etc.
- the molded body is excellent in light source concealment. Therefore, the haze of the molded body is preferably 99% or more.
- Example 1 Manufacture of seed particles
- 250 g of methyl methacrylate as a monofunctional vinyl monomer (first vinyl monomer) and 5 g of n-octyl mercaptan as a chain transfer agent were mixed to prepare 255 g of a monomer mixture. did.
- 1.5 g of potassium persulfate as a polymerization initiator was dissolved in 18.5 g of deionized water as an aqueous medium to obtain 20 g of an aqueous potassium persulfate solution.
- an emulsion containing seed particles (polymethyl methacrylate particles) was obtained.
- the volume average particle diameter of the seed particles contained in the obtained emulsion was 0.38 ⁇ m.
- the mass average molecular weight (Mw) of the seed particles contained in the obtained emulsion was 15,300.
- n-butyl acrylate as a monofunctional vinyl monomer (second vinyl monomer) and ethylene glycol dimer as a crosslinkable monomer (second vinyl monomer)
- methacrylate 28% by mass with respect to the total mass of the resin particles
- n-dodecyl mercaptan as a chain transfer agent
- 2,2′-azobisisobutyronitrile as a polymerization initiator
- a dispersion was obtained by stirring the contents of the polymerization vessel with a high-speed emulsification / dispersing machine “TK homomixer” manufactured by PRIMIX Corporation. At this time, the diameter of the droplets (droplets of the mixed liquid) in the dispersion liquid was adjusted by adjusting the agitation, and a dispersion liquid having a droplet diameter of about 5 ⁇ m was prepared.
- the emulsion containing the seed particles was added to the dispersion, and the monomer mixture was absorbed by the seed particles. Thereafter, the contents of the polymerization vessel were stirred with the stirrer under a nitrogen stream, and the polymerization was carried out over 5 hours by raising the internal temperature of the polymerization vessel to 50 ° C. and keeping it at 50 ° C. for 5 hours. Thereafter, the internal temperature of the polymerization vessel was cooled to room temperature (about 25 ° C.). As a result, a slurry containing resin particles was obtained.
- the obtained slurry was passed through a stainless steel wire mesh having a mesh size of 20 ⁇ m to classify resin particles, thereby obtaining a slurry containing classified resin particles.
- the volume average particle diameter D1 of the resin particles contained in the obtained slurry was 1.1 ⁇ m, and the coefficient of variation of the particle diameter of the resin particles contained in the obtained slurry was 12.5%.
- the obtained slurry has a solid content concentration of 28% by mass, and the surfactant content is 2.3 parts by mass with respect to 100 parts by mass of the resin particles.
- the estimated value of the refractive index of the obtained resin particle aggregate was 1.48.
- the obtained resin particle aggregate had a volume average particle diameter D3 of 52 ⁇ m.
- the obtained resin particle aggregate does not contain an inorganic component.
- the volume average particle diameter D2 of the particles contained in the resin particle assembly dispersion liquid is 6.5 ⁇ m, and the volume of the particles contained in the resin particle assembly dispersion liquid with respect to the volume average particle diameter D1 of the resin particles.
- Example 2 Manufacture of seed particles
- the seed particles produced in Example 1 were used.
- n-butyl methacrylate as a monofunctional vinyl monomer (second vinyl monomer) and ethylene glycol dimer as a crosslinkable monomer (second vinyl monomer) 120 g of methacrylate (38% by mass with respect to the total mass of the resin particles), 3 g of n-dodecyl mercaptan as a chain transfer agent, and 2 g of 2,2′-azobisisobutyronitrile as a polymerization initiator are mixed.
- 305 g of a monomer mixed solution was obtained.
- 900 g of the surfactant aqueous solution was put into a polymerization vessel equipped with a stirrer and a thermometer, and then 305 g of the monomer mixed solution was put into the polymerization vessel.
- a dispersion was obtained by stirring the contents of the polymerization vessel with a high-speed emulsification / dispersing machine “TK homomixer” manufactured by PRIMIX Corporation.
- the diameter of the droplets (droplets of the mixed liquid) in the dispersion liquid was adjusted by adjusting the agitation, and a dispersion liquid having a droplet diameter of about 5 ⁇ m was prepared.
- the internal temperature of the polymerization vessel was raised to 50 ° C. and kept at 50 ° C. for 10 hours to carry out polymerization for 10 hours. Thereafter, the internal temperature of the polymerization vessel was cooled to room temperature (about 25 ° C.). As a result, a slurry containing resin particles was obtained.
- the obtained slurry was passed through a stainless steel wire mesh having a mesh size of 20 ⁇ m to classify resin particles, thereby obtaining a slurry containing classified resin particles.
- the volume average particle diameter D1 of the resin particles contained in the obtained slurry was 1.2 ⁇ m, and the variation coefficient of the particle diameter of the resin particles contained in the obtained slurry was 17.3%.
- the obtained slurry has a solid concentration of 25% by mass, and the content of the surfactant is 1.9 parts by mass with respect to 100 parts by mass of the resin particles.
- a resin particle aggregate was produced under the same conditions as in Example 1 except that the resin particles obtained in this example were used in place of the resin particles in Example 1.
- the estimated value of refractive index of the obtained resin particle aggregate was 1.49.
- the obtained resin particle aggregate had a volume average particle diameter D3 of 55 ⁇ m.
- the obtained resin particle aggregate does not contain an inorganic component.
- the volume average particle diameter D2 of the particles contained in the resin particle assembly dispersion is 5.7 ⁇ m
- the volume of the particles contained in the resin particle assembly dispersion with respect to the volume average particle diameter D1 of the resin particles is 4.8
- a molded body made of the light diffusing resin composition was produced under the same conditions as in Example 1 except that the resin particle aggregate obtained in this example was used in place of the resin particle aggregate in Example 1.
- the obtained molded article had a total light transmittance of 67%, and the obtained molded article had a haze of 99%.
- Example 3 Manufacture of seed particles 250 g of styrene as a monofunctional vinyl monomer (first vinyl monomer) and 5 g of ⁇ -methylstyrene dimer as a chain transfer agent were mixed to prepare 255 g of a monomer mixture. Further, 1.5 g of potassium persulfate as a polymerization initiator was dissolved in 18.5 g of deionized water as an aqueous medium to obtain 20 g of an aqueous potassium persulfate solution.
- an emulsion containing seed particles (polystyrene particles) was obtained.
- the volume average particle diameter of the seed particles contained in the obtained emulsion was 0.40 ⁇ m.
- the mass average molecular weight (Mw) of the seed particles contained in the obtained emulsion was 13,500.
- styrene as a monofunctional vinyl monomer (second vinyl monomer) and 30 g of ethylene glycol dimethacrylate as a crosslinkable monomer (second vinyl monomer) (resin 9.6% by mass with respect to the total mass of the particles) and 1.5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator are mixed, and the monomer mixture 301 .5 g was obtained.
- 900 g of the surfactant aqueous solution was put into a polymerization vessel equipped with a stirrer and a thermometer, and then 301.5 g of the monomer mixed solution was put into the polymerization vessel.
- a dispersion was obtained by stirring the contents of the polymerization vessel with a high-speed emulsification / dispersing machine “TK homomixer” manufactured by PRIMIX Corporation.
- the diameter of the droplets (droplets of the mixed liquid) in the dispersion liquid was adjusted by adjusting the agitation, and a dispersion liquid having a droplet diameter of about 5 ⁇ m was prepared.
- the emulsion containing the seed particles was added to the dispersion, and the monomer mixture was absorbed by the seed particles. Thereafter, the contents of the polymerization vessel were stirred with the stirrer under a nitrogen stream, and the polymerization was carried out over 5 hours by raising the internal temperature of the polymerization vessel to 50 ° C. and keeping it at 50 ° C. for 5 hours. Thereafter, the internal temperature of the polymerization vessel was cooled to room temperature (about 25 ° C.). As a result, a slurry containing resin particles was obtained.
- the obtained slurry was passed through a stainless steel wire mesh having a mesh size of 20 ⁇ m to classify resin particles, thereby obtaining a slurry containing classified resin particles.
- the volume average particle diameter D1 of the resin particles contained in the obtained slurry was 1.2 ⁇ m, and the coefficient of variation of the particle diameter of the resin particles contained in the obtained slurry was 11.3%.
- the obtained slurry has a solid concentration of 25% by mass, and the content of the surfactant is 1.9 parts by mass with respect to 100 parts by mass of the resin particles.
- the estimated value of the refractive index of the obtained resin particle aggregate was 1.58.
- the obtained resin particle aggregate had a volume average particle diameter D3 of 53 ⁇ m.
- the obtained resin particle aggregate does not contain an inorganic component.
- the volume average particle diameter D2 of the particles contained in the resin particle assembly dispersion is 6.3 ⁇ m, and the volume of the particles contained in the resin particle assembly dispersion with respect to the volume average particle diameter D1 of the resin particles.
- the resin particle aggregate obtained in this example was used in place of the resin particle aggregate of Example 1, and polymethyl methacrylate (Sumipex EXA, manufactured by Sumitomo Chemical Co., Ltd.) instead of polystyrene as the transparent base resin. ) was used under the same conditions as in Example 1 to produce a molded article made of the light diffusing resin composition.
- the obtained molded article had a total light transmittance of 66%, and the obtained molded article had a haze of 99%.
- Example 4 Manufacture of seed particles
- the seed particles produced in Example 3 were used.
- a dispersion was obtained by stirring the contents of the polymerization vessel with a high-speed emulsification / dispersing machine “TK homomixer” manufactured by PRIMIX Corporation. At this time, the diameter of the droplets (droplets of the mixed liquid) in the dispersion liquid was adjusted by adjusting the agitation, and a dispersion liquid having a droplet diameter of about 5 ⁇ m was prepared.
- the obtained slurry was passed through a stainless steel wire mesh having a mesh size of 20 ⁇ m to classify resin particles, thereby obtaining a slurry containing classified resin particles.
- the volume average particle diameter D1 of the resin particles contained in the obtained slurry was 1.1 ⁇ m, and the coefficient of variation of the particle diameter of the resin particles contained in the obtained slurry was 13.7%.
- the obtained slurry has a solid content concentration of 32% by mass, and the surfactant content is 1.9 parts by mass with respect to 100 parts by mass of the resin particles.
- a resin particle aggregate was obtained under the same conditions as in Example 3 except that the resin particles obtained in this example were used in place of the resin particles in Example 3.
- the estimated value of the refractive index of the obtained resin particle aggregate was 1.59.
- the obtained resin particle aggregate had a volume average particle diameter D3 of 52 ⁇ m.
- the obtained resin particle aggregate does not contain an inorganic component.
- the volume average particle diameter D2 of the particles contained in the resin particle assembly dispersion is 5.8 ⁇ m, and the volume of the particles contained in the resin particle assembly dispersion with respect to the volume average particle diameter D1 of the resin particles.
- a plate-like molded body having a thickness of 2 mm, a width of 50 mm, and a length of 100 mm was obtained as a molded body made of the composition.
- the obtained molded article had a total light transmittance of 65%, and the obtained molded article had a haze of 99%.
- Example 5 Manufacture of seed particles
- 200 g of methyl methacrylate as a monofunctional vinyl monomer (first vinyl monomer) and 6 g of n-octyl mercaptan as a chain transfer agent were mixed to obtain 206 g of a monomer mixture.
- 1.5 g of potassium persulfate as a polymerization initiator was dissolved in 18.5 g of deionized water as an aqueous medium to obtain 20 g of an aqueous potassium persulfate solution.
- an emulsion containing seed particles (polymethyl methacrylate particles) was obtained.
- the volume average particle diameter of the seed particles contained in the obtained emulsion was 0.30 ⁇ m.
- the mass average molecular weight (Mw) of the seed particles contained in the obtained emulsion was 12,900.
- n-butyl acrylate as a monofunctional vinyl monomer (second vinyl monomer) and ethylene glycol dimer as a crosslinkable monomer (second vinyl monomer) 160 g of methacrylate (49% by mass with respect to the total mass of the resin particles), 4 g of n-dodecyl mercaptan as a chain transfer agent, 2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator, Were mixed to obtain 306 g of a monomer mixed solution.
- the obtained slurry was passed through a stainless steel wire mesh having a mesh size of 20 ⁇ m to classify resin particles, thereby obtaining a slurry containing classified resin particles.
- the volume average particle diameter D1 of the resin particles contained in the obtained slurry was 0.86 ⁇ m, and the coefficient of variation of the particle diameter of the resin particles contained in the obtained slurry was 14.1%.
- the obtained slurry has a solid content concentration of 27% by mass, and the surfactant content is 3.1 parts by mass with respect to 100 parts by mass of the resin particles.
- the estimated value of the refractive index of the obtained resin particle aggregate was 1.48.
- the obtained resin particle aggregate had a volume average particle diameter D3 of 52 ⁇ m.
- the obtained resin particle aggregate does not contain an inorganic component.
- the volume average particle diameter D2 of the particles contained in the resin particle assembly dispersion is 5.7 ⁇ m
- the volume of the particles contained in the resin particle assembly dispersion with respect to the volume average particle diameter D1 of the resin particles is 6.6
- the obtained resin particle aggregate was imaged by SEM, and the SEM image of FIG. 1 was obtained. From FIG. 1, it was found that the obtained resin particle aggregate is a resin particle aggregate having a spherical outer shape. Further, as a result of observing the resin particle aggregate with a TEM, the obtained resin particle aggregate is present in a state where the seed particle component and the component obtained by polymerization of the monomer mixture are uniformly mixed. It was found to have one structure. Therefore, the obtained resin particle aggregate was neither a core-shell type particle nor an inclined structure whose composition gradually changed from the center toward the outside.
- the obtained resin particle aggregate is not a core-shell type particle having a core and a shell having different refractive indexes, but has an inclined structure in which the refractive index gradually changes from the center toward the outside. Rather, it is considered to have a single refractive index.
- a molded body made of the light diffusing resin composition was produced under the same conditions as in Example 1 except that the resin particle aggregate obtained in this example was used in place of the resin particle aggregate in Example 1.
- the obtained molded article had a total light transmittance of 63%, and the obtained molded article had a haze of 99%.
- Example 6 Manufacture of seed particles
- the seed particles produced in Example 5 were used.
- methyl methacrylate as a monofunctional vinyl monomer (second vinyl monomer) and 40 g of ethylene glycol dimethacrylate as a crosslinkable monomer (second vinyl monomer) (18% by mass with respect to the total mass of the resin particles), 2 g of n-dodecyl mercaptan as a chain transfer agent, and 1.5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator Were mixed to obtain 203.5 g of a monomer mixture.
- a dispersion was obtained by stirring the contents of the polymerization vessel with a high-speed emulsification / dispersing machine “TK homomixer” manufactured by PRIMIX Corporation. At this time, the diameter of the droplets (droplets of the mixed liquid) in the dispersion liquid was adjusted by adjusting the agitation, and a dispersion liquid having a droplet diameter of about 5 ⁇ m was prepared.
- the obtained slurry was passed through a stainless steel wire mesh having a mesh size of 20 ⁇ m to classify resin particles, thereby obtaining a slurry containing classified resin particles.
- the volume average particle diameter D1 of the resin particles contained in the obtained slurry was 0.62 ⁇ m, and the variation coefficient of the particle diameter of the resin particles contained in the obtained slurry was 17.9%.
- the obtained slurry has a solid content concentration of 24% by mass, and the surfactant content is 1.4 parts by mass with respect to 100 parts by mass of the resin particles.
- the volume average particle diameter D2 of the particles contained in the resin particle assembly dispersion is 6.6 ⁇ m
- the obtained resin particle aggregate was imaged with SEM, and the SEM image of FIG. 2 was obtained. From FIG. 2, it was found that the obtained resin particle aggregate is a resin particle aggregate having a spherical outer shape.
- Example 1 Manufacture of molded products
- a molded body was prepared under the same conditions as in Example 1 except that the resin particle aggregate obtained in this example was used and polycarbonate (Panlite, manufactured by Teijin Chemicals Ltd.) was used as the base resin.
- the total light transmittance and haze of the obtained molded body were measured. The results are shown in Table 1.
- the resin particle aggregate obtained in this example was used in place of the resin particle aggregate in Example 1, and polycarbonate instead of polystyrene as the transparent base resin (“Panlite”, manufactured by Teijin Chemicals Ltd.)
- a molded body made of a light diffusing resin composition was produced under the same conditions as in Example 1 except that was used.
- the obtained molded article had a total light transmittance of 63%, and the obtained molded article had a haze of 99%.
- the obtained slurry was passed through a stainless steel wire mesh having a mesh size of 20 ⁇ m to classify resin particles, thereby obtaining a slurry containing classified resin particles.
- the volume average particle diameter D1 of the resin particles contained in the obtained slurry was 1.2 ⁇ m, and the coefficient of variation of the particle diameter of the resin particles contained in the obtained slurry was 12.0%.
- a resin particle aggregate was obtained under the same conditions as in Example 1 except that the resin particles obtained in this Comparative Example were used in place of the resin particles in Example 1.
- the estimated value of the refractive index of the obtained resin particle aggregate was 1.47.
- the obtained resin particle aggregate had a volume average particle diameter D3 of 52 ⁇ m.
- the volume average particle diameter D2 of the particles contained in the resin particle assembly dispersion is 34 ⁇ m
- the ratio of was 18.2% by volume.
- a molded body made of the light diffusing resin composition was produced under the same conditions as in Example 1 except that the resin particle aggregate obtained in this Comparative Example was used in place of the resin particle aggregate in Example 1.
- the obtained molded article had a total light transmittance of 68%, and the obtained molded article had a haze of 98%.
- n-butyl acrylate as a monofunctional vinyl monomer (second vinyl monomer) and ethylene glycol dimer as a crosslinkable monomer (second vinyl monomer)
- 96 g of methacrylate, 3.2 g of n-dodecyl mercaptan as a chain transfer agent, and 1.6 g of 2,2′-azobisisobutyronitrile as a polymerization initiator are mixed, and a monomer mixture 324. 8 g was obtained.
- 320 g of the surfactant aqueous solution was put into a polymerization vessel equipped with a stirrer and a thermometer, and then 324.8 g of the monomer mixed solution was put into the polymerization vessel.
- a dispersion was obtained by stirring the contents of the polymerization vessel with a high-speed emulsification / dispersing machine “TK homomixer” manufactured by PRIMIX Corporation.
- the diameter of the droplets (droplets of the mixed liquid) in the dispersion liquid was adjusted by adjusting the agitation, and a dispersion liquid having a droplet diameter of about 5 ⁇ m was prepared.
- the obtained slurry was passed through a stainless steel wire mesh having a mesh size of 20 ⁇ m to classify resin particles, thereby obtaining a slurry containing classified resin particles.
- the volume average particle diameter D1 of the resin particles contained in the obtained slurry was 1.1 ⁇ m, and the coefficient of variation of the particle diameter of the resin particles contained in the obtained slurry was 11.1%.
- the obtained slurry has a solid content of 48% by mass, and the surfactant content is 0.8 parts by mass with respect to 100 parts by mass of the resin particles.
- a resin particle aggregate was produced under the same conditions as in Example 1 except that the resin particles produced in this comparative example were used.
- the estimated value of refractive index of the obtained resin particle aggregate was 1.48.
- the obtained resin particle aggregate had a volume average particle diameter D3 of 54 ⁇ m.
- the volume average particle diameter D2 of the particles contained in the resin particle assembly dispersion is 35 ⁇ m
- the ratio was 20.8% by volume.
- Example 2 Manufacture of molded products
- a molded body was produced under the same conditions as in Example 1 except that the resin particle aggregate produced in this comparative example was used.
- the obtained molded article had a total light transmittance of 69%, and the obtained molded article had a haze of 98%.
- the volume average particle diameter of the seed particles contained in the obtained emulsion was 0.44 ⁇ m.
- the emulsion containing the seed particles was added to the dispersion, and the mixture was stirred at 30 ° C. for 1 hour to allow the seed particles to absorb the monomer mixture.
- the absorbed monomer mixture was polymerized by heating at 50 ° C. for 5 hours under a nitrogen stream, and then cooled to room temperature (about 25 ° C.). Thereby, a slurry containing resin particles was obtained.
- the obtained slurry was passed through a stainless steel wire mesh having a mesh size of 20 ⁇ m to classify resin particles, thereby obtaining a slurry containing classified resin particles.
- the volume average particle diameter D1 of the resin particles contained in the obtained slurry was 1.2 ⁇ m, and the coefficient of variation of the particle diameter of the resin particles contained in the obtained slurry was 12.3%.
- a spray dryer (model: atomizer system and take-up system, model number: TRS-3WK) manufactured by Sakamoto Giken Co., Ltd. as a spray dryer, slurry supply rate: 25 ml / min, atomizer rotation Number: 11000 rpm, air volume: 2 m 3 / min, inlet temperature (temperature of slurry inlet): 130 ° C., outlet temperature (temperature of powder outlet): 70 ° C. Got.
- the estimated value of the refractive index of the obtained resin particle aggregate was 1.48.
- the obtained resin particle aggregate had a volume average particle diameter D3 of 51 ⁇ m.
- the content of the inorganic component in the obtained resin particle aggregate is 8.7% by mass.
- the volume average particle diameter D2 of the particles contained in the resin particle assembly dispersion is 30 ⁇ m
- the ratio D2 / D1 of the diameter D2 is 2.7
- the particles having a particle diameter larger than the volume average particle diameter D3 ( 51 ⁇ m) of the resin particle aggregate in the particles contained in the resin particle aggregate dispersion liquid
- the ratio was 0.0 vol%.
- the resin particle aggregate retained a spherical shape, and the connection of the resin particles by fusion of the resin particles was not confirmed.
- composition of the second vinyl monomer constituting the resin particles in Examples 1 to 6 and Comparative Examples 1 to 4), the volume average particle diameter D1 of the resin particles, the coefficient of variation of the particle diameter, the resin particle aggregate Volume average particle diameter D3, volume average particle diameter D2 of particles contained in resin particle assembly dispersion, ratio D2 / D1, dispersibility evaluation value (resin particles in particles contained in resin particle assembly dispersion Table 1 summarizes the ratio of particles having a particle diameter larger than the volume average particle diameter D3 of the aggregate), the composition of the molded body (type and amount of base resin), and the total light transmittance and haze of the molded body. Show.
- BA represents butyl acrylate
- EDMA represents ethylene glycol dimethacrylate
- BMA represents butyl methacrylate
- ST represents styrene
- DVB represents divinylbenzene
- MMA represents methyl methacrylate
- PMMA represents polymethyl methacrylate.
- the resin particle aggregates according to Examples 1 to 6 of the present invention are resin particle aggregates of Comparative Example 1 in which the resin particles are crosslinked with a crosslinkable monomer of less than 9% by mass.
- the ratio D2 / D1 is 15 or less, and the dispersibility evaluation value is 1. It was found that it was less than mass% and easily dispersed in primary particles or a state close thereto.
- the resin particle aggregates according to Examples 1 to 6 of the present invention are easily dispersed into primary particles or a state close to the primary particles, good light intensity is obtained when blended with a light diffusing composition (molded article). It was found that diffusibility (haze) was imparted.
- the resin particle aggregates according to Examples 1 to 6 of the present invention have an inorganic content of more than 0.5% by mass when blended with the light diffusing composition (molded product). As compared with the resin particle aggregate of Comparative Example 2 containing components, it was found that good light transmittance (total light transmittance) was given.
- Example 7 (Production Example of Coating Composition) 25 parts by mass of the particle aggregate obtained in Example 1 and a commercially available alkyd resin as a binder resin (oil-free alkyd resin manufactured by DIC Corporation, trade name “Beckolite (registered trademark) M-6402-50”) (solvent) 100% by mass of 50% by mass), 30 parts by mass of xylene as a solvent, and 5 parts by mass of carbon black as a color pigment are manufactured by Shinky Co., Ltd.
- the coating composition as one type of the coating composition was obtained by stirring (mixing) for 10 minutes followed by degassing for 1 minute.
- the coating composition obtained was applied onto a polyester film using a coating apparatus on which a blade having a clearance of 100 ⁇ m was set, and then dried to obtain a coating film.
- Example 8 Example of production of optical film 250 parts by mass of the resin particle aggregate produced in Example 1 and ACRICID (trademark pending) A-801-P (acrylic polyol; manufactured by DIC Corporation, solid content 50% by mass, hydroxyl value 50 mgKOH as a binder resin / G) 180 parts by mass and Takenate D110N (polyisocyanate; manufactured by Mitsui Chemicals, solid content 60% by mass), 300 parts by mass of toluene as a solvent and 330 parts by mass of methyl ethyl ketone (MEK) A light diffusing ink was obtained as a coating composition.
- ACRICID trademark pending
- the light diffusing ink is coated on a PET (polyethylene terephthalate) film having a thickness of 100 ⁇ m by a die coating method to form a light diffusing layer having a thickness of 12 ⁇ m (light diffusing ink is cured).
- a light diffusing film provided with a layer).
- Example 9 (Production example of optical film) First, 100 parts by mass of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate as a binder resin (KAYARAD PET-30, manufactured by Nippon Kayaku Co., Ltd.), and 15 parts by mass of the resin particle assembly produced in Example 1 Then, 6 parts by mass of an ultraviolet polymerization initiator (manufactured by Ciba Specialty Chemicals, Inc., Irgacure 184) and 140 parts by mass of toluene as a solvent were mixed to obtain a mixture. The mixture was dispersed in a sand mill for 30 minutes to obtain a light diffusion layer forming composition as a coating composition.
- a binder resin KAYARAD PET-30, manufactured by Nippon Kayaku Co., Ltd.
- the composition for forming a light diffusion layer was applied to one side of a TAC (triacetylcellulose) film having a thickness of 80 ⁇ m by a gravure reverse coating method and dried at 100 ° C. for 2 minutes. Thereafter, the coating film is irradiated with ultraviolet light with a single 120 W / cm condensing high-pressure mercury lamp, and the coating film is cured, whereby a light diffusion layer (light diffusion layer forming composition) having a layer thickness of 6 ⁇ m is obtained. An antiglare film having a layer formed by curing the product was obtained.
- TAC triacetylcellulose
- Example 10 (Production example of external preparation)
- a powder foundation comprising a powder part and an oil part was produced. That is, first, 21 g of the particle aggregate obtained in Example 1, 38 g of talc as a clay mineral, 22 g of mica as a clay mineral, 6 g of titanium oxide as a color material, and red as a color material 0.6 g of iron oxide, 1 g of yellow iron oxide as a color material material, and 0.1 g of black iron oxide as a color material material were mixed with a Henschel mixer to prepare the powder part.
- the oil part (excluding fragrance) was added to the powder part and mixed uniformly. Furthermore, after adding 0.1 g of fragrance
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Abstract
Description
前記方法によれば、噴霧乾燥に用いるスラリーの固形分濃度が高いので、噴霧乾燥によって蒸発させる水の量が少ないので、噴霧乾燥にかかる時間が短く、製造効率を向上できる。
前記構成の外用剤は、本発明の樹脂粒子集合体を混合しているので、前記樹脂粒子集合体が一次粒子またはそれに近い状態となって分散しており、透明外用剤の場合には良好なソフトフォーカス効果および光透過性を有し、不透明外用剤の場合には良好な艶消し性を有する。
本発明の樹脂粒子集合体は、ビニル系単量体の重合体からなる樹脂粒子(一次粒子)が複数、集合(凝集)することによって形成された樹脂粒子集合体であって、前記樹脂粒子100質量部と、界面活性剤1~5質量部とを含み、前記樹脂粒子は、前記樹脂粒子の全質量に対して9~50質量%の架橋性単量体で架橋されており、前記樹脂粒子集合体中における無機成分の含有量が0.5質量%以下であり、前記樹脂粒子の体積平均粒子径D1に対する、前記樹脂粒子集合体を水に分散させた分散液中に含まれる粒子の体積平均粒子径D2の比D2/D1が15以下である樹脂粒子集合体である。ここで、前記体積平均粒子径D2は、前記樹脂粒子集合体0.50gと水50gとを混合し、これらの混合物に出力400W、周波数20kHzの超音波分散機を用いて超音波を10分間照射することにより分散液を得た後、前記樹脂粒子の屈折率に合わせた光学モデルを使用して粒子の体積平均粒子径を算出するレーザー回折散乱法粒度分布測定装置により、前記分散液中に含まれる粒子の体積平均粒子径を測定する測定方法で測定されたものである。
本発明で用いられる前記単官能性ビニル系単量体は、重合可能なアルケニル基(広義のビニル基)を1分子中に1つ有する化合物である。前記単官能性ビニル系単量体としては、例えば、芳香族ビニル単量体;(メタ)アクリル酸エステル単量体、ハロゲン化ビニル単量体、シアン化ビニル系単量体等が使用できる。前記芳香族ビニル単量体としては、例えば、スチレン、α-メチルスチレン等のスチレン類(スチレン系単量体)等が使用できる。前記(メタ)アクリル酸エステル単量体としては、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-プロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸tert-ブチル、(メタ)アクリル酸n-ペンチル、(メタ)アクリル酸n-ヘキシル等の(メタ)アクリル酸アルキル等が使用できる。これら単官能性ビニル系単量体は、単独で用いてもよく2種以上を組み合わせて用いてもよい。これら単官能性ビニル系単量体のうち、スチレン類および(メタ)アクリル酸アルキル((メタ)アクリル酸アルキル系単量体)から選ばれる少なくとも1種の単量体が好ましく、スチレンおよびアルキル基の炭素数が1~4である(メタ)アクリル酸アルキルから選ばれる少なくとも1種の単量体がより好ましい。これにより、良好な全光線透過率を有する樹脂粒子集合体を実現できる。単官能性ビニル系単量体が、アルキル基の炭素数が5以上の(メタ)アクリル酸アルキルである場合、樹脂粒子が融着しやすくなり、一次粒子になりにくくなるため、好ましくない
なお、本明細書において、「(メタ)アクリル」はアクリルまたはメタクリルを意味し、「(メタ)アクリレート」はアクリレートまたはメタクリレートを意味するものとする。
種粒子の質量平均分子量(Mw)は、50,000以下であることが好ましい。種粒子の質量平均分子量が50,000を超える場合、種粒子が第2のビニル系単量体を吸収しにくくなり、得られる樹脂粒子の粒度分布が広がってしまう。樹脂粒子の粒度分布が広がると、粒子同士の接触箇所が増えるため、樹脂粒子間の融着が起こり易くなり、樹脂粒子集合体が一次粒子またはそれに近い状態に分散しにくくなる。また、樹脂粒子の粒度分布が広がると、本発明の樹脂粒子集合体を他の成分と混合したときに、樹脂粒子の光拡散性や艶消し等の特性が不均一となり易い。
樹脂粒子を構成するビニル系単量体の全質量に対する種粒子の割合、すなわち樹脂粒子の全質量に対する種粒子の割合は、10質量%以下であることが好ましい。種粒子が非架橋または微架橋である場合、樹脂粒子の全質量に対する種粒子の割合が10質量%を超えると、ガラス転移温度の低い種粒子が、樹脂粒子の乾燥時に溶融して、樹脂粒子同士を融着させる要因となるため、好ましくない。なお、樹脂粒子の全質量に対する種粒子の割合は、樹脂粒子中の種粒子を溶媒で溶解させることによって分析できる。
次に、本発明の樹脂粒子集合体を製造するのに適した方法である、本発明の製造方法について説明する。本発明の製造方法は、第1のビニル系単量体の重合体からなる種粒子に第2のビニル系単量体を吸収させ、第2のビニル系単量体を重合させるシード重合法によって樹脂粒子を得るシード重合工程と、得られた樹脂粒子100質量部と、界面活性剤1~5質量部と、水性媒体とを含むスラリーを、前記スラリーが噴霧されて導入されるスラリー入口および前記樹脂粒子集合体が排出される粉体出口を備える噴霧乾燥機により、スラリー入口の温度が80℃~220℃の範囲内、粉体出口の温度が40℃~100℃の範囲内の条件で噴霧乾燥する噴霧乾燥工程とを含み、前記第2のビニル系単量体の重合時に、水溶性高分子を使用せず、前記樹脂粒子が、前記樹脂粒子100質量%に対して9~50質量%の架橋性単量体を含み、前記スラリーの固形分濃度が24~40質量%の範囲内である。
なお、第2のビニル系単量体の重合に使用する重合開始剤は界面活性剤濃度が臨界ミセル濃度以上である場合、過酸化ベンゾイル、2,2’-アゾビスイソブチロニトリル等の油溶性重合開始剤を使用するのが好ましい。第2のビニル系単量体の重合では、油溶性重合開始剤を使用した場合、過硫酸カリウムなどの水溶性重合開始剤を使用した場合と比較して、目的とする樹脂粒子以外の新粒子が発生することを抑制できる。
本発明の光拡散性樹脂組成物は、透明基材樹脂と、光拡散剤としての本発明の樹脂粒子集合体とを混合してなるものである。
本発明の光拡散性樹脂組成物を構成する透明基材樹脂としては、通常、透明性の高い熱可塑性樹脂が使用される。前記透明基材樹脂としては、例えば、ポリメタクリル酸メチル等の(メタ)アクリル樹脂(ポリ(メタ)アクリル酸エステル)、(メタ)アクリル酸アルキル-スチレン共重合体、ポリカーボネート、ポリエステル、ポリエチレン、ポリプロピレン、ポリスチレン等の熱可塑性樹脂が挙げられる。これら熱可塑性樹脂の中でも、優れた透明性が求められる場合には、(メタ)アクリル樹脂、(メタ)アクリル酸アルキル-スチレン共重合体、ポリカーボネート、ポリエステル、およびポリスチレンが好ましい。これら熱可塑性樹脂は、単独で用いてもよく2種以上を組み合わせて用いてもよい。
光拡散性樹脂組成物の製造方法は、特に限定されず、例えば、本発明の樹脂粒子集合体と透明基材樹脂とを、機械式粉砕混合方法等のような混合方法で混合することによって、光拡散性樹脂組成物を製造できる。機械式粉砕混合方法では、例えばヘンシェルミキサー、V型混合機、ターブラミキサー、ハイブリダイザー、ロッキングミキサー等を用いて混合および攪拌を行うことができる。
本発明の樹脂粒子集合体は、塗料用艶消し剤、光拡散フィルム用光拡散剤、防眩フィルム用粒子等としてコーティング用組成物に含有させることが可能である。本発明のコーティング用組成物は、本発明の樹脂粒子集合体を他の成分と配合してなるものである。
本発明の光学フィルムは、本発明のコーティング用組成物を基材フィルム上にコーティングして得られるものである。本発明の光学フィルムは、防眩フィルム、光拡散フィルム等として利用できる。
本発明の樹脂粒子集合体は、外用剤の原料としても使用できる。本発明の外用剤は、本発明の樹脂粒子集合体を他の成分と配合してなる。外用剤における樹脂粒子集合体の含有量は、外用剤の種類に応じて適宜設定できるが、1~80質量%の範囲内であることが好ましく、5~70質量%の範囲内であることがより好ましい。外用剤全量に対する樹脂粒子集合体の含有量が1質量%を下回ると、樹脂粒子集合体の含有による明確な効果が認められないことがある。また、樹脂粒子集合体の含有量が80質量%を上回ると、含有量の増加に見合った顕著な効果が認められないことがあるため、生産コスト上好ましくない。
種粒子の質量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)を用いて測定した。測定した質量平均分子量は、ポリスチレン(PS)換算質量平均分子量である。その測定方法は、次の通りである。まず、試料50mgをテトラヒドロフラン(THF)10mlに溶解させた。得られた溶液を0.45μmの非水系クロマトディスクを用いて濾過した。得られた濾液をGPCにより分析し、PS換算質量平均分子量を測定した。GPCの測定条件は、下記の通りとした。
カラム:東ソー株式会社製の商品名「TSKgel GMH XL-L」(直径7.8mm×長さ30cm)2本
カラム温度:40℃
キャリアーガス:テトラヒドロフラン(THF)
キャリアーガス流量:1mL/分
注入・ポンプ温度:35℃
検出:RI(示差屈折率検出器)
注入量:100μL
PS換算質量平均分子量を算出するための検量線用標準ポリスチレン:昭和電工株式会社製の商品名「shodex」(質量平均分子量:1030000)および東ソー株式会社製の検量線用標準ポリスチレン(質量平均分子量:5480000、3840000、355000、102000、37900、9100、2630、870)
〔種粒子および樹脂粒子の体積平均粒子径、並びに樹脂粒子の変動係数の測定方法〕
以下の実施例および比較例において、種粒子および樹脂粒子の体積平均粒子径は、以下のようにして測定した。すなわち、種粒子および樹脂粒子の体積平均粒子径は、ベックマン・コールター株式会社製のレーザー回折散乱粒度分布測定装置「LS230」型で測定した。具体的には、測定対象粒子(種粒子または樹脂粒子)0.1gを試験管内に取り、0.1質量%ノニオン性界面活性剤(モノラウリン酸ポリオキシエチレンソルビタン(エチレンオキシド付加モル数20)、商品名「レオドールTW-L120」、花王株式会社製)水溶液10mlを前記測定対象粒子に加え、前記水溶液と前記測定対象粒子とをヤマト科学株式会社製のマグミキサ(タッチミキサ)「MT-31」型で2秒間混合した。その後、この試験管を、市販の超音波洗浄器である株式会社ヴェルヴォクリーア製の卓上型超音波洗浄器「VS-150」に入れ、この超音波洗浄器で前記試験管に超音波を10分間照射することにより、前記測定対象粒子を前記水溶液中に分散させて、分散液を得た。
なお、このレーザー回折散乱粒度分布測定装置は、測定対象粒子の屈折率に合わせた光学モデルを使用して粒子の回折・散乱光の空間強度分布データを解析することによって粒子の体積平均粒子径および粒度分布を算出するものであるので、測定対象粒子の屈折率の入力を必要とする。ここでは、前記データ解析に使用する測定対象粒子の屈折率として屈折率の推算値をレーザー回折散乱粒度分布測定装置に入力した。測定対象粒子の製造に1種類のビニル系単量体を用いた場合には、そのビニル系単量体の単独重合体の屈折率を測定対象粒子の屈折率の推算値として用いた。測定対象粒子の製造に複数種類のビニル系単量体を用いた場合には、各ビニル系単量体の単独重合体の屈折率を各ビニル系単量体の使用量で加重平均した平均値を測定対象粒子の屈折率の推算値として用いた。
以下の実施例および比較例において、樹脂粒子集合体の体積平均粒子径は、以下のようにして測定した。すなわち、樹脂粒子集合体の体積平均粒子径は、ベックマン・コールター株式会社製のレーザー回折散乱粒度分布測定装置「LS230」型で測定した。具体的には、粒子(種粒子または樹脂粒子)0.1gを試験管内に取り、0.1質量%ノニオン性界面活性剤(モノラウリン酸ポリオキシエチレンソルビタン(エチレンオキシド付加モル数20)、商品名「レオドールTW-L120」、花王株式会社製)水溶液10mlを前記樹脂粒子集合体に加え、前記水溶液と前記樹脂粒子集合体とをヤマト科学株式会社製のマグミキサ(タッチミキサ)「MT-31」型で2秒間混合し、混合液を得た。
以下の実施例および比較例では、樹脂粒子集合体の1次粒子またはそれに近い状態への分散性を評価するための2種類の評価値として、樹脂粒子の体積平均粒子径D1に対する、樹脂粒子集合体を水に分散させた分散液(以下、「樹脂粒子集合体分散液」と呼ぶ)中に含まれる粒子の体積平均粒子径D2の比D2/D1と、樹脂粒子集合体分散液中に含まれる粒子中における、樹脂粒子集合体の体積平均粒子径D3よりも大きい粒子径を有する粒子の割合とを、以下のようにして測定した。
以下の実施例および比較例において、成形体の全光線透過率は、日本電色工業株式会社製のヘーズメーター「NDH 2000」を使用して、JIS K7361(プラスチック-透明材料の全光線透過率の試験方法-第1部:シングルビーム法)に従って測定した。また、以下の実施例および比較例において、成形体のヘーズは、日本電色工業株式会社製のヘーズメーター「NDH 2000」を使用して、JIS K7136-1(プラスチック-透明材料のヘーズの求め方)に従って測定した。具体的には、日本電色工業社製NDH-2000を使用して測定する。成形体のヘーズが99%以上である場合、前記成形体の光拡散性が高いので、前記成形体を液晶バックライトユニットに組み込んだとき、前記成形体を照明カバーとして照明器具に取り付けたときなどに、前記成形体が、光源の隠蔽性に優れる。したがって、成形体のヘーズは、99%以上であることが好ましい。
(種粒子の製造)
まず、単官能性ビニル系単量体(第1のビニル系単量体)としてのメタクリル酸メチル250gと連鎖移動剤としてのn-オクチルメルカプタン5gとを混合して、単量体混合物255gを調製した。また、重合開始剤としての過硫酸カリウム1.5gを水性媒体としての脱イオン水18.5gに溶解させて、過硫酸カリウム水溶液20gを得た。
まず、界面活性剤としてのジオクチルスルホコハク酸ナトリウム8gを水性媒体としての脱イオン水782gに溶解させて、界面活性剤水溶液800gを得た。また、単官能性ビニル系単量体(第2のビニル系単量体)としてのアクリル酸n-ブチル224gと、架橋性単量体(第2のビニル系単量体)としてのエチレングリコールジメタクリレート96g(樹脂粒子の全質量に対して28質量%)と、連鎖移動剤としてのn-ドデシルメルカプタン3.2gと、重合開始剤としての2,2’-アゾビスイソブチロニトリル1.6gとを混合して、単量体混合液324.8gを得た。
前記樹脂粒子を含むスラリーを、噴霧乾燥機としての株式会社坂本技研製のスプレードライヤー(型式:アトマイザ方式かつテイクアップ方式、型番:TRS-3WK)を用いて、スラリーの供給速度:25ml/min、アトマイザ回転数:11000rpm、風量:2m3/min、入口温度(スプレードライヤーに備えられた、スラリーが噴霧されて導入されるスラリー入口の温度):150℃、出口温度(スプレードライヤーに備えられた、樹脂粒子集合体が排出される粉体出口の温度):70℃の条件下にて噴霧乾燥することにより、樹脂粒子集合体を得た。
透明基材樹脂としてのポリスチレン(東洋スチレン株式会社製の「トーヨースチロール(登録商標)GP G200C」)100質量部と、前記樹脂粒子集合体1質量部とを、押出機中に供給し、押出機中にて230℃で溶融および混練した後、ペレット化した。得られたペレットを、射出成形機を用いてシリンダー温度230℃、滞留時間10分の条件で成形することにより、光拡散性樹脂組成物からなる成形体として、厚さ2mm×幅50mm×長さ100mmの板状の成形体(光拡散板)を得た。得られた成形体の全光線透過率は65%、得られた成形体のヘーズは99%であった。
(種粒子の製造)
実施例1で製造した種粒子を使用した。
まず、界面活性剤としてのジオクチルスルホコハク酸ナトリウム6gを水性媒体としての脱イオン水894gに溶解させて、界面活性剤水溶液900gを得た。また、単官能性ビニル系単量体(第2のビニル系単量体)としてのメタクリル酸n-ブチル180gと、架橋性単量体(第2のビニル系単量体)としてのエチレングリコールジメタクリレート120g(樹脂粒子の全質量に対して38質量%)と、連鎖移動剤としてのn-ドデシルメルカプタン3gと、重合開始剤としての2,2’-アゾビスイソブチロニトリル2gとを混合して、単量体混合液305gを得た。
実施例1の樹脂粒子に代えて本実施例で得られた樹脂粒子を使用した以外は実施例1と同様の条件で、樹脂粒子集合体を製造した。
実施例1の樹脂粒子集合体に代えて本実施例で得られた樹脂粒子集合体を使用した以外は実施例1と同様の条件で、光拡散性樹脂組成物からなる成形体を製造した。得られた成形体の全光線透過率は67%、得られた成形体のヘーズは99%であった。
(種粒子の製造)
単官能性ビニル系単量体(第1のビニル系単量体)としてのスチレン250gと連鎖移動剤としてのα-メチルスチレンダイマー5gとを混合して、単量体混合物255gを調製した。また、重合開始剤としての過硫酸カリウム1.5gを水性媒体としての脱イオン水18.5gに溶解させて、過硫酸カリウム水溶液20gを得た。
まず、界面活性剤としてのポリオキシエチレンアルキルフェニルエーテルリン酸ナトリウム6gを水性媒体としての脱イオン水894gに溶解させて、界面活性剤水溶液900gを得た。また、単官能性ビニル系単量体(第2のビニル系単量体)としてのスチレン270gと、架橋性単量体(第2のビニル系単量体)としてのエチレングリコールジメタクリレート30g(樹脂粒子の全質量に対して9.6質量%)と、重合開始剤としての2,2’-アゾビス(2,4-ジメチルバレロニトリル)1.5gとを混合して、単量体混合液301.5gを得た。
前記樹脂粒子を含むスラリーを、噴霧乾燥機としての株式会社坂本技研製のスプレードライヤー(型式:アトマイザ方式かつテイクアップ方式、型番:TRS-3WK)を用いて、スラリーの供給速度:25ml/min、アトマイザ回転数:15000rpm、風量:2m3/min、入口温度(スラリー入口の温度):180℃、出口温度(粉体出口の温度):90℃の条件下にて噴霧乾燥することにより、樹脂粒子集合体を得た。
実施例1の樹脂粒子集合体に代えて本実施例で得られた樹脂粒子集合体を使用したこと、および透明基材樹脂としてポリスチレンに代えてポリメタクリル酸メチル(スミペックスEXA、住友化学株式会社製)を使用したこと以外は、実施例1と同様の条件で、光拡散性樹脂組成物からなる成形体を製造した。得られた成形体の全光線透過率は66%、得られた成形体のヘーズは99%であった。
(種粒子の製造)
実施例3で製造した種粒子を使用した。
まず、界面活性剤としてのジオクチルスルホコハク酸ナトリウム4gおよびポリオキシエチレンアルキルフェニルエーテルリン酸ナトリウム4gを脱イオン水792gに溶解させて、界面活性剤水溶液800gを得た。また、単官能性ビニル系単量体(第2のビニル系単量体)としてのスチレン350gと、架橋性単量体(第2のビニル系単量体)としてのジビニルベンゼン50g(樹脂粒子の全質量に対して12質量%)と、重合開始剤としての過酸化ベンゾイル2gとを混合して、単量体混合液402gを得た。
実施例3の樹脂粒子に代えて本実施例で得られた樹脂粒子を使用した以外は実施例3と同様の条件で、樹脂粒子集合体を得た。
透明基材樹脂としてのポリスチレン(東洋スチレン株式会社製の「トーヨースチロール(登録商標)GP G200C」)100質量部と、前記樹脂粒子集合体50質量部とを、押出機中に供給し、押出機中にて230℃で溶融および混練した後、ペレット化した。得られたペレット3質量部とポリスチレン98質量部とを混合し、得られた混合物を、射出成形機を用いてシリンダー温度230℃、滞留時間10分の条件で成形することにより、光拡散性樹脂組成物からなる成形体として、厚さ2mm×幅50mm×長さ100mmの板状の成形体を得た。得られた成形体の全光線透過率は65%、得られた成形体のヘーズは99%であった。
(種粒子の製造)
まず、単官能性ビニル系単量体(第1のビニル系単量体)としてのメタクリル酸メチル200gと、連鎖移動剤としてのn-オクチルメルカプタン6gとを混合して、単量体混合物206gを調製した。また、重合開始剤としての過硫酸カリウム1.5gを水性媒体としての脱イオン水18.5gに溶解させて、過硫酸カリウム水溶液20gを得た。
まず、界面活性剤としてのジオクチルスルホコハク酸ナトリウム10gを水性媒体としての脱イオン水790gに溶解させて、界面活性剤水溶液800gを得た。また、単官能性ビニル系単量体(第2のビニル系単量体)としてのアクリル酸n-ブチル240gと、架橋性単量体(第2のビニル系単量体)としてのエチレングリコールジメタクリレート160g(樹脂粒子の全質量に対して49質量%)と、連鎖移動剤としてのn-ドデシルメルカプタン4gと、重合開始剤として2,2’-アゾビス(2,4-ジメチルバレロニトリル)2gとを混合して、単量体混合液306gを得た。
前記樹脂粒子を含むスラリーを、噴霧乾燥機としての株式会社坂本技研製のスプレードライヤー(型式:アトマイザ方式かつテイクアップ方式、型番:TRS-3WK)を用いて、スラリーの供給速度:25ml/min、アトマイザ回転数:13000rpm、風量:2m3/min、入口温度(スラリー入口の温度):150℃、出口温度(粉体出口の温度):70℃の条件下にて噴霧乾燥することにより、樹脂粒子集合体を得た。
実施例1の樹脂粒子集合体に代えて本実施例で得られた樹脂粒子集合体を使用した以外は実施例1と同様の条件で、光拡散性樹脂組成物からなる成形体を製造した。得られた成形体の全光線透過率は63%、得られた成形体のヘーズは99%であった。
(種粒子の製造)
実施例5にて製造した種粒子を使用した。
まず、界面活性剤としてのジオクチルスルホコハク酸ナトリウム3gを脱イオン水597gに溶解させて、界面活性剤水溶液600gを得た。また、単官能性ビニル系単量体(第2のビニル系単量体)としてのメタクリル酸メチル160gと、架橋性単量体(第2のビニル系単量体)としてのエチレングリコールジメタクリレート40g(樹脂粒子の全質量に対して18質量%)と、連鎖移動剤としてのn-ドデシルメルカプタン2gと、重合開始剤としての2,2’-アゾビス(2,4-ジメチルバレロニトリル)1.5gとを混合して、単量体混合液203.5gを得た。
前記樹脂粒子を含むスラリーを、噴霧乾燥機としての株式会社坂本技研製のスプレードライヤー(型式:アトマイザ方式かつテイクアップ方式、型番:TRS-3WK)を用いて、スラリーの供給速度:25ml/min、アトマイザ回転数:13000rpm、風量:2m3/min、入口温度(スラリー入口の温度):170℃、出口温度(粉体出口の温度):90℃の条件下にて噴霧乾燥することにより、樹脂粒子集合体を得た。得られた樹脂粒子集合体の屈折率の推算値は、1.49であった。得られた樹脂粒子集合体の体積平均粒子径D3は50μmであった。得られた樹脂粒子集合体は、無機成分を含有していない。
本実施例で得られた樹脂粒子集合体を使用し、基材樹脂としてポリカーボネート(パンライト、帝人化成社製)を使用した以外は実施例1と同様の条件で成型体を作成した。得られた成形体の全光線透過率およびヘーズを測定した。結果を表1に示す。
(種粒子の製造)
実施例1と同様の条件で種粒子を製造した。
アクリル酸n-ブチルの量を304gに変更したこと、およびエチレングリコールジメタクリレートの量を16g(樹脂粒子の全質量に対して4.7質量%)に変更したこと以外は、実施例1と同様にして、樹脂粒子を製造した。
実施例1の樹脂粒子に代えて本比較例で得られた樹脂粒子を使用した以外は実施例1と同様の条件で樹脂粒子集合体を得た。得られた樹脂粒子集合体の屈折率の推算値は、1.47であった。得られた樹脂粒子集合体の体積平均粒子径D3は52μmであった。
実施例1の樹脂粒子集合体に代えて本比較例で得られた樹脂粒子集合体を使用した以外は実施例1と同様の条件で、光拡散性樹脂組成物からなる成形体を製造した。得られた成形体の全光線透過率は68%、得られた成形体のヘーズは98%であった。
(種粒子の製造)
実施例1と同様の条件で種粒子を製造した。
まず、界面活性剤としてのジオクチルスルホコハク酸ナトリウム3gを脱イオン水317gに溶解させて、界面活性剤水溶液320gを得た。また、単官能性ビニル系単量体(第2のビニル系単量体)としてのアクリル酸n-ブチル224gと、架橋性単量体(第2のビニル系単量体)としてのエチレングリコールジメタクリレート96gと、連鎖移動剤としてのn-ドデシルメルカプタン3.2gと、重合開始剤としての2,2’-アゾビスイソブチロニトリル1.6gとを混合して、単量体混合液324.8gを得た。
本比較例で製造した樹脂粒子を用いる以外は、実施例1と同様の条件で樹脂粒子集合体を製造した。得られた樹脂粒子集合体の屈折率の推算値は、1.48であった。得られた樹脂粒子集合体の体積平均粒子径D3は54μmであった。
本比較例で製造した樹脂粒子集合体を用いる以外は実施例1と同様の条件で、成形体を製造した。得られた成形体の全光線透過率全光線透過率は69%、得られた成形体のヘーズは98%であった。
(種粒子の製造)
実施例3と同様の条件で種粒子を製造した。
スチレンの量を160gに変更したこと、およびジビニルベンゼンの量を240gに変更したこと以外は、実施例4と同様にして重合を行った。その結果、重合時に粒子が凝集して樹脂粒子は得られなかった。SEMで観察したところ、1μm程度の粒子同士が融着していた。このため、樹脂粒子集合体は製造できなかった。また、樹脂粒子の体積平均粒子径D1および粒子径の変動係数は測定できなかった。
(種粒子の製造)
まず、重合開始剤としての過硫酸カリウム1gを水性媒体としての脱イオン水19gに溶解させて、過硫酸カリウム水溶液20gを得た。攪拌機および温度計を備えた重合器に水性媒体としての脱イオン水1000gを入れ、さらに、単官能性ビニル系単量体(第1のビニル系単量体)としてのメタクリル酸メチル200gと、連鎖移動剤としてのtert-ドデシルメルカプタン6gとを前記重合器に供給した。続いて、前記重合器の内容物を前記攪拌機により攪拌しながら、前記重合器内の空気を窒素で置換し、前記重合器の内温を70℃まで昇温した。さらに、前記攪拌を継続し、かつ前記重合器の内温を70℃に保ちながら、重合開始剤としての前記過硫酸カリウム水溶液20gを前記重合器の内容物に添加した後、10時間かけて重合を行った。
まず、界面活性剤としてのポリオキシエチレントリデシルエーテル硫酸アンモニム3gを脱イオン水795gに溶解させて、界面活性剤水溶液800gを得た。また、単官能性ビニル系単量体(第2のビニル系単量体)としてのアクリルn-酸ブチル160gと、架橋性単量体(第2のビニル系単量体)としてのエチレングリコールジメタクリレート40gと、重合開始剤としての2,2’-アゾビスイソブチロニトリル1gとを混合して、単量体混合液201gを得た。
前記樹脂粒子を含むスラリーに、「スノーテックスO-40」(日産化学工業株式会社製:コロイダルシリカ(無機粉末)として固形分40%、粒子径:0.02-0.03μm)50gを加え、プライミクス株式会社製の高速乳化・分散機「T.K.ホモミクサー」にて10分間攪拌した。得られたスラリーは、固形分濃度が21質量%である。
透明基材樹脂としてのポリスチレン(東洋スチレン株式会社製の「トーヨースチロール(登録商標)GP G200C」)100質量部と、前記樹脂粒子集合体1質量部とを、押出機中に供給し、押出機中にて230℃で溶融および混練した後、ペレット化した。ペレット化時にメヤニの発生は見られなかった。得られたペレットを、射出成形機を用いてシリンダー温度230℃、滞留時間10分の条件で成形することにより、光拡散性樹脂組成物からなる成形体として、厚さ2mm×幅50mm×長さ100mmの板状の成形体を得た。得られた成形体の全光線透過率は60%、得られた成形体のヘーズは99%であった。
〔実施例7〕(コーティング用組成物の製造例)
実施例1で得た粒子集合体25質量部と、バインダー樹脂としての市販のアルキド樹脂(DIC株式会社製オイルフリーアルキド樹脂、商品名「ベッコライト(登録商標)M-6402-50」)(溶剤含有量50質量%)100質量部と、溶剤としてのキシレン30質量部と、着色顔料としてのカーボンブラック5質量部とを、攪拌脱泡装置である株式会社シンキー製の「あわとり練太郎(登録商標)」を用いて、10分間攪拌(混合)し、続いて1分間脱泡することによって、コーティング用組成物の1種としての塗料組成物を得た。クリアランス100μmのブレードをセットした塗工装置を用いて、得られた塗料組成物をポリエステルフィルム上に塗布した後、乾燥することによって塗膜を得た。
実施例1で製造した樹脂粒子集合体250質量部と、バインダー樹脂としてのアクリディック(出願中の商標)A-801-P(アクリルポリオール;DIC株式会社製、固形分50質量%、水酸基価50mgKOH/g)180質量部およびタケネートD110N(ポリイソシアネート;三井化学株式会社製、固形分60質量%)50質量部と、溶剤としてのトルエン300質量部およびメチルエチルケトン(MEK)330質量部とを混合して、コーティング用組成物としての光拡散性インキを得た。
まず、バインダー樹脂としてのペンタエリスリトールトリアクリレートとペンタエリスリトールテトラアクリレートとの混合物(KAYARAD PET-30、日本化薬株式会社製)100質量部と、実施例1で製造した樹脂粒子集合体15質量部と、紫外線重合開始剤(チバ・スペシャリティケミカルズ株式会社製、イルガキュア184)6質量部と、溶剤としてのトルエン140質量部とを混合し、混合物を得た。前記混合物をサンドミルにて30分間分散することによって、コーティング用組成物としての光拡散層形成用組成物を得た。厚さ80μmのTAC(トリアセチルセルロース)フィルムの片面に、前記光拡散層形成用組成物をグラビアリバースコート法で塗布し、100℃で2分間乾燥した。その後、120W/cmの集光型高圧水銀灯1灯で塗工膜に紫外線照射を行い、塗工膜を硬化させることにより、光学フィルムとして、層厚6μmの光拡散層(光拡散層形成用組成物が硬化することによって形成された層)を備えた防眩フィルムを得た。
本例では、粉体部およびオイル部からなるパウダーファンデーションを製造した。すなわち、まず、実施例1で得た粒子集合体21gと、粘土鉱物類としてのタルク38gと、粘土鉱物類としてのマイカ22gと、色材原料としての酸化チタン6gと、色材原料としての赤色酸化鉄0.6gと、色材原料としての黄色酸化鉄1gと、色材原料としての黒色酸化鉄0.1gとをヘンシェルミキサーで混合して、前記粉体部を調製した。また、脂肪酸エステルとしての2-エチルヘキサン酸セチル10gと、界面活性剤としてのソルビタンセスキオレエート1gと、防腐剤0.2gとを混合溶解して、オイル部(香料を除く)を調製した。
Claims (14)
- ビニル系単量体の重合体からなる樹脂粒子が複数、集合することによって形成された樹脂粒子集合体であって、
前記樹脂粒子100質量部と、
界面活性剤1~5質量部とを含み、
前記樹脂粒子は、前記樹脂粒子の全質量に対して9~50質量%の架橋性単量体で架橋されており、
前記樹脂粒子集合体中における無機成分の含有量が0.5質量%以下であり、
前記樹脂粒子の体積平均粒子径D1に対する、前記樹脂粒子集合体を水に分散させた分散液中に含まれる粒子の体積平均粒子径D2の比D2/D1が15以下であり、
前記体積平均粒子径D2は、前記樹脂粒子集合体0.50gと水50gとを混合し、これらの混合物に出力400W、周波数20kHzの超音波分散機を用いて超音波を10分間照射することにより分散液を得た後、前記樹脂粒子の屈折率に合わせた光学モデルを使用して粒子の体積平均粒子径を算出するレーザー回折散乱法粒度分布測定装置により、前記分散液中に含まれる粒子の体積平均粒子径を測定する測定方法で測定されたものであることを特徴とする樹脂粒子集合体。 - 請求項1に記載の樹脂粒子集合体であって、
前記樹脂粒子集合体を水に分散させた分散液中に含まれる粒子中における、前記樹脂粒子集合体の体積平均粒子径D3よりも大きい粒子径を有する粒子の割合が1体積%以下であり、
前記割合は、前記樹脂粒子集合体0.50gと水50gとを混合し、これらの混合物に出力400W、周波数20kHzの超音波分散機を用いて超音波を10分間照射することにより分散液を得た後、前記樹脂粒子の屈折率に合わせた光学モデルを使用して粒子の体積平均粒子径を算出するレーザー回折散乱法粒度分布測定装置により、前記分散液中に含まれる粒子の体積基準の粒度分布を測定し、測定された体積基準の粒度分布と前記樹脂粒子集合体の体積平均粒子径D3とから前記割合を算出する測定方法で測定されたものであることを特徴とする樹脂粒子集合体。 - 請求項1に記載の樹脂粒子集合体であって、
前記ビニル系単量体が、スチレン系単量体および(メタ)アクリル酸アルキル系単量体からなる群より選ばれる少なくとも1種の単量体であることを特徴とする請求項1に記載の樹脂粒子集合体。 - 請求項1に記載の樹脂粒子集合体であって、
前記架橋性単量体が、ジビニルベンゼン、エチレングリコールジ(メタ)アクリレート、およびトリメチロールプロパントリ(メタ)アクリレートからなる群より選ばれる少なくとも1種の単量体である樹脂粒子集合体。 - 請求項1に記載の樹脂粒子集合体であって、
第1のビニル系単量体の重合体からなる種粒子に第2のビニル系単量体を吸収させ、第2のビニル系単量体を重合させるシード重合法によって得られたものであることを特徴とする樹脂粒子集合体。 - 請求項5に記載の樹脂粒子集合体であって、
前記樹脂粒子の全質量に対する種粒子の割合が10質量%以下であることを特徴とする樹脂粒子集合体。 - 請求項1に記載の樹脂粒子集合体であって、
前記樹脂粒子の体積平均粒子径が0.1~2.0μmであり、
前記樹脂粒子の粒子径の変動係数が20%以下であることを特徴とする樹脂粒子集合体。 - 第1のビニル系単量体の重合体からなる種粒子に第2のビニル系単量体を吸収させ、第2のビニル系単量体を重合させるシード重合法によって樹脂粒子を得るシード重合工程と、
得られた樹脂粒子100質量部と、界面活性剤1~5質量部と、水性媒体とを含むスラリーを、前記スラリーが噴霧されて導入されるスラリー入口および前記樹脂粒子集合体が排出される粉体出口を備える噴霧乾燥機により、スラリー入口の温度が80℃~220℃の範囲内、粉体出口の温度が40℃~100℃の範囲内の条件で噴霧乾燥する噴霧乾燥工程とを含み、
前記第2のビニル系単量体の重合時に、水溶性高分子を使用せず、
前記樹脂粒子が、前記樹脂粒子100質量%に対して9~50質量%の架橋性単量体を含み、
前記スラリーの固形分濃度が24~40質量%の範囲内であることを特徴とする樹脂粒子集合体の製造方法。 - 請求項8に記載の樹脂粒子集合体の製造方法であって、
前記シード重合工程の後に前記樹脂粒子を分級し、分級された樹脂粒子を前記噴霧乾燥工程に用いることを特徴とする樹脂粒子集合体の製造方法。 - 請求項8または9に記載の樹脂粒子集合体の製造方法であって、
前記スラリー中における無機成分の含有量が、前記樹脂粒子の全質量に対して0.5質量%以下であることを特徴とする樹脂粒子集合体の製造方法。 - 透明基材樹脂と、請求項1~7の何れか1項に記載の樹脂粒子集合体とを混合してなることを特徴とする光拡散性樹脂組成物。
- 請求項1~7の何れか1項に記載の樹脂粒子集合体を配合してなることを特徴とするコーティング用組成物。
- 請求項12に記載のコーティング用組成物を基材フィルム上にコーティングして得られることを特徴とする光学フィルム。
- 請求項1~7の何れか1項に記載の樹脂粒子集合体を配合してなることを特徴とする外用剤。
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